Resin particle and method for prepartion thereof

ABSTRACT

A method for preparing a resin particle having a large surface area and a shape factor (SF-1) of 110 to 800, which comprises a step of applying a shear force to an aqueous dispersion having a viscosity of 300 to 100,000 mPa·s formed by adding a thickener to an aqueous dispersion containing resin particles, and a subsequent step of decreasing the viscosity of the aqueous dispersion to 200 mPa·s or less by adding a viscosity decreasing agent as necessary. Resin particles obtained by the method can be used as additives for paint, additives for coating materials, powder coatings, additives for cosmetics, resins for slush molding, spacers for use in manufacturing electronic components or devices, standard particles for electronic measuring instruments, toners for electrophotography, toners for electrostatic recording, toners for electrostatic printing, and hot-melt adhesives.

TECHNICAL FIELD

The present invention relates to a resin particle and method forpreparation thereof. More particularly, the present invention relates toresin particles which can be of use as additives for paints, additivesfor coating materials, powder coatings, additives for cosmetics, resinsfor slush molding, spacers for manufacturing electronic components ordevices such as liquid crystal displays, standard particles forelectronic measuring instruments, toners for electrophotography,electrostatic recording, or electrostatic printing, hot-melt adhesives,other molding materials, and the like, and to method for preparing thesame.

BACKGROUND ART

There are known resin particles prepared by a method in which a resinsolution, obtained by dissolving a resin in a solvent, is dispersed inan aqueous medium under the presence of a dispersing (assistant) agentsuch as a surfactant or a water-soluble polymer and then the solvent isremoved by heating or decompression (that is, by a method of suspendinga resin solution in an aqueous medium: see Japanese Patent Laid-open No.Hei 9-34167, for example).

In general, as resin particles obtained by such a method of suspending aresin solution in an aqueous medium are spherical particles, such resinparticles have a drawback that the fluidity thereof tends to becomeexcessive and the surface area thereof is small. Therefore, in a casewhere the resin particles are used as an additive for paint, obtainedpaint has a problem that the kinematic viscosity thereof is lowered,resulting in poor coating properties. Further, in a case where the resinparticles are used as a toner, there is a problem that cleaning of thetoner with a cleaning blade is not satisfactorily carried out.

It is therefore an object of the present invention to provide anon-spherical resin particle (e.g., a spindle- or rod-shaped resinparticle), and a method for preparing such resin particles.

DISCLOSURE OF THE INVENTION

The present inventors have earnestly studied to solve theabove-described problem, thereby leading to the present invention. Thepresent invention is a method for preparing resin particles, comprisinga step of applying a shear force to an aqueous dispersion (II) withincreased viscosity formed by adding a thickener (V) to an aqueousdispersion (I) containing resin particles (A) and a subsequent step ofdecreasing the viscosity of the aqueous dispersion by adding a viscositydecreasing agent (E) when it is required, and resin particles (B)obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

In polyaddition reaction and curing reaction, a well-known catalyst orthe like can be used.

A resin particle (A) to be used in the present invention comprises aresin (a). The resin (a) may be either a thermoplastic resin or athermosetting resin, and examples of the resin (a) include vinyl resins,polyurethanes, epoxy resins, polyesters, polyamides, polyimides,silicone resins, phenolic resins, melamine resins, urea resins, anilineresins, ionomer resins, polycarbonates, and mixtures of two or more ofthem. Among them, from the viewpoint of obtaining uniform and finespherical resin particles easily, vinyl resins, polyurethanes, epoxyresins, polyesters, and mixtures of two or more of them are preferred,vinyl resins, polyurethanes, polyesters, and mixtures of two or more ofthem are more preferred, and vinyl resins, polyesters, and mixtures oftwo or more of them are even more preferred.

Hereinbelow, these resins to be preferably used as the resin (a), thatis, vinyl resins, polyurethanes, epoxy resins, and polyesters will bedescribed, but the other resins mentioned above can also be used as theresin (a).

Vinyl resins are homopolymers or copolymers of vinyl monomers.

In polymerization, a well-known polymerization catalyst or the like canbe used.

As vinyl monomers, the following compounds (1) to (10) can be used.

(1) Vinyl Hydrocarbons:

(1-1) Aliphatic Vinyl Hydrocarbons:

-   -   alkenes having 2 to 12 carbon atoms (e.g., ethylene, propylene,        butene, isobutylene, pentene, heptene, diisobutylene, octene,        dodecene, octadecene, and α-olefins having 3 to 24 carbon        atoms); and alkadienes having 4 to 12 carbon atoms (e.g.,        butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, and        1,7-octadiene).

(1-2) Alicyclic Vinyl Hydrocarbons:

-   -   mono- or di-cycloalkenes having 6 to 15 carbon atoms (e.g.,        cyclohexene, vinylcyclohexene, and ethylidenebicycloheptene);        mono- or di-cycloalkadienes having 5 to 12 carbon atoms (e.g.,        (di)cyclopentadiene); terpenes (e.g., pinene, limonene, and        indene); and the like.

(1-3) Aromatic Vinyl Hydrocarbons:

-   -   styrene; hydrocarbyl(alkyl, cycloalkyl, aralkyl, and/or alkenyl        each having 1 to 24 carbon atoms)-substituted styrene (e.g.,        α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene,        ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene,        cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene,        divinyltoluene, divinylxylene, and trivinylbenzene);        vinylnaphthalene; and the like.

(2) Carboxyl Group-Containing Vinyl Monomers and Salts Thereof:

-   -   unsaturated monocarboxylic acids having 3 to 30 carbon atoms        (e.g., (meth)acrylic acid, crotonic acid, isocrotonic acid and        cinnamic acid); unsaturated dicarboxylic acids having 3 to 30        carbon atoms or anhydrides thereof (e.g., maleic acid        (anhydride), fumaric acid, itaconic acid, citraconic acid        (anhydride), and mesaconic acid); monoalkyl (having 1 to 24        carbon atoms) esters of unsaturated dicarboxylic acids having 3        to 30 carbon atoms (e.g., monomethyl ester of maleic acid,        monooctadecyl ester of maleic acid, monoethyl ester of fumaric        acid, monobutyl ester of itaconic acid, glycol monoether of        itaconic acid, and monoeicosyl ester of citraconic acid); and        the like.

Examples of salts of the carboxyl group-containing vinyl monomersinclude alkali metal salts (e.g., sodium salts and potassium salts),alkaline-earth metal salts (e.g., calcium salts and magnesium salts),ammonium salts, amine salts, and quaternary ammonium salts. The aminesalts are not limited to any specific ones as long as they are aminecompounds, but primary amine salts (e.g., ethylamine salts, butylaminesalts, and octylamine salts), secondary amine salts (e.g., diethylaminesalts and dibutylamine salts), and tertiary amine salts (e.g.,triethylamine salts and tributylamine salts) can be mentioned, forexample. As the quaternary ammonium salts, tetraethylammonium salts,lauryltriethylammonium salts, tetrabutylammonium salts,lauryltributylammonium salts, and the like can be mentioned.

Specific examples of salts of the carboxyl group-containing vinylmonomers include sodium acrylate, sodium methacrylate, monosodiummaleate, disodium maleate, potassium acrylate, potassium methacrylate,monopotassium maleate, lithium acrylate, cesium acrylate, ammoniumacrylate, calcium acrylate, aluminum acrylate, and the like.

(3) Sulfo Group-Containing Vinyl Monomers and Salts Thereof:

-   -   alkenesulfonic acids having 2 to 14 carbon atoms (e.g.,        vinylsulfonic acid, (meth)allylsulfonic acid, and        methylvinylsulfonic acid); styrenesulfonic acid and alkyl        (having 2 to 24 carbon atoms) derivatives thereof (e.g.,        α-methylstyrenesulfonic acid);        sulfo(hydroxy)alkyl-(meth)acrylates having 5 to 18 carbon atoms        (e.g., sulfopropyl(meth)acrylate,        2-hydroxy-3-(meth)acryloxypropylsulfonic acid,        2-(meth)acryloyloxyethanesulfonic acid, and        3-(meth)acryloyloxy-2-hydroxypropanesulfoic acid);        sulfo(hydroxy)alkyl(meth)acrylamides having 5 to 18 carbon atoms        (e.g., 2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid,        2-(meth)acrylamide-2-methylpropanesulfonic acid, and        3-(meth)acrylamide-2-hydroxypropanesulfonic acid); alkyl (having        3 to 18 carbon atoms) allylsulfosuccinic acids (e.g.,        propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, and        2-ethylhexyl-allylsulfosuccinic acid); poly(n=2 to 30)        oxyalkylene (oxyethylene, oxypropylene, oxybutylene: homo,        random, or block)mono(meth)acrylate sulfates (e.g., poly(n=5 to        15)oxyethylene monomethacrylate sulfate and poly(n=5 to        15)oxypropylene monomethacrylate sulfate); polyoxyethylene        polycyclic phenyl ether sulfates (e.g., sulfates represented by        the general formula (1-1) or (1-2)); sulfonic acids represented        by the general formula (1-3)); salts thereof; and the like.

It is to be noted that counter ions mentioned with reference to “(2)carboxyl group-containing vinyl monomers and salts thereof” or the likeare used for the salts.

-   -   wherein R represents an alkyl group having 1 to 15 carbon atoms,        AO represents an oxyalkylene group having 2 to 4 carbon atoms,        and wherein when n is plural, oxyalkylene groups may be the same        or different, and when different, they may be random, block        and/or combination of random and block, Ar represents a benzene        ring, n is an integer of 1 to 50, and R′ represents an alkyl        group having 1 to 15 carbon atoms which may be substituted by a        fluorine atom.

(4) Phosphono Group-Containing Vinyl Monomers and salts Thereof:

-   -   (meth)acryloyloxyalkyl (having 1 to 24 carbon atoms)        monophosphates (e.g., 2-hydroxyethyl(meth)acryloyl phosphate and        phenyl-2-acryloyloxyethyl phosphate), and (meth)acryloyloxyalkyl        (having 1 to 24 carbon atoms)phosphonic acids (e.g.,        2-acryloyloxyethylphosphonic acid).

(5) Hydroxyl Group-Containing Vinyl Monomers:

-   -   hydroxystyrene, N-methylol(meth)acrylamide,        hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,        polyethylene glycol mono(meth)acrylate, (meth)allyl alcohol,        crotyl alcohol, isocrotyl alcohol, 1-butene-3-ol, 2-butene-1-ol,        2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethyl propenyl        ether, and allyl ether of sucrose, and the like.

(6) Nitrogen-Containing Vinyl Monomers:

(6-1) Amino Group-Containing Vinyl Monomers:

-   -   aminoethyl(meth)acrylate, dimethylaminoethyl (meth)acrylate,        diethylaminoethyl(meth)acrylate, t-butylaminoethyl methacrylate,        N-aminoethyl(meth)acrylamide, (meth)allylamine,        morpholinoethyl(meth)acrylate, 4-vinylpyridine, 2-vinylpyridine,        crotylamine, N,N-dimethylaminostyrene, methyl        α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole,        N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole,        aminothiazole, aminoindole, aminopyrrole, aminoimidazole,        aminomercaptothiazole, salts thereof, and the like.

(6-2) Amide Group-Containing Vinyl Monomers:

-   -   (meth)acrylamide, N-methyl(meth)acrylamide, N-butylacrylamide,        diacetoneacrylamide, N-methylol(meth)acrylamide,        N,N′-methylene-bis(meth)acrylamide, cinnamamide,        N,N-dimethylacrylamide, N,N-dibenzylacrylamide, methacryl        formamide, N-methyl-N-vinylacetamide, and N-vinylpyrrolidone,        and the like.

(6-3) Nitrile Group-Containing Vinyl Monomers Having 3 to 10 CarbonAtoms:

-   -   (meth)acrylonitrile, cyanostyrene, cyanoacrylate, and the like.

(6-4) Quaternary Ammonium Cation Group-Containing Vinyl Monomers:

-   -   quaternization products (obtained using a quaternizing agent        such as methyl chloride, dimethyl sulfate, benzyl chloride,        dimethyl carbonate or the like) of tertiary amine        group-containing vinyl monomers such as dimethylaminoethyl        (meth)acrylate, diethylaminoethyl(meth)acrylate,        dimethylaminoethyl(meth)acrylamide,        diethylaminoethyl(meth)acrylamide, diallylamine, and the like        (e.g., dimethyldiallylammonium chloride and        trimethylallylammonium chloride).

(6-5) Nitro Group-Containing Vinyl Monomers Having 8 to 12 Carbon Atoms:

-   -   nitrostyrene and the like.

(7) Epoxy Group-Containing Vinyl Monomers Having 6 to 18 Carbon Atoms:

-   -   glycidyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate,        p-vinylphenyl oxide, and the like.

(8) Halogen-Containing Vinyl Monomers Having 2 to 16 Carbon Atoms:

-   -   vinyl chloride, vinyl bromide, vinylidene chloride, allyl        chloride, chlorostyrene, bromostyrene, dichlorostyrene,        chloromethylstyrene, tetrafluorostyrene, chloroprene, and the        like.

(9) Vinyl Esters, Vinyl(Thio)Ethers, Vinyl Ketones, and Vinyl Sulfones:

(9-1) Vinyl Esters Having 4 to 16 Carbon Atoms:

-   -   vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate,        diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl        methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate,        benzyl methacrylate, phenyl (meth)acrylate, vinyl        methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate,        alkyl(meth)acrylates having an alkyl group containing 1 to 50        carbon atoms (e.g., methyl(meth)acrylate, ethyl(meth)acrylate,        propyl(meth)acrylate, butyl (meth)acrylate,        2-ethylhexyl(meth)acrylate, dodecyl (meth)acrylate,        hexadecyl(meth)acrylate, heptadecyl (meth)acrylate, and        eicosyl(meth)acrylate), dialkyl fumarates (whose two alkyl        groups are straight, branched or alicyclic groups having 2 to 8        carbon atoms), dialkyl maleates (whose two alkyl groups are        straight, branched or alicyclic groups having 2 to 8 carbon        atoms), poly(meth)allyloxyalkanes (e.g., diallyloxyethane,        triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane,        tetraallyloxybutane, and tetramethallyloxyethane), vinyl-based        monomers having a polyalkylene glycol chain [e.g., polyethylene        glycol (molecular weight: 300) mono(meth)acrylate, polypropylene        glycol (molecular weight: 500) monoacrylate, methyl        alcohol-ethylene oxide (10 mol) adduct (meth)acrylate, and        lauryl alcohol-ethylene oxide (30 mol) adduct (meth)acrylate],        and poly(meth)acrylates (e.g., poly(meth)acrylates of polyhydric        alcohols: ethylene glycol di(meth)acrylate, propylene glycol        di(meth)acrylate, neopentyl glycol di(meth)acrylate,        trimethylolpropane tri(meth)acrylate, and polyethylene glycol        di(meth)acrylate), and the like.

(9-2) Vinyl(Thio)Ethers Having 3 to 16 Carbon Atoms:

-   -   vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl        butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl        2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl        ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether,        vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, and        phenoxystyrene, and the like.

(9-3) Vinyl ketones having 4 to 12 carbon atoms (e.g., vinyl methylketone, vinyl ethyl ketone, and vinyl phenyl ketone), vinyl sulfoneshaving 2 to 16 carbon atoms (e.g., divinyl sulfide, p-vinyl diphenylsulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, anddivinyl sulfoxide), and the like.

(10) Other Vinyl Monomers:

-   -   isocyanatoethyl(meth)acrylate, m-isopropenyl-α, α-dimethylbenzyl        isocyanate, and the like.

Among these vinyl monomers, vinyl hydrocarbons, carboxylgroup-containing vinyl monomers and salts thereof, sulfonic acidgroup-containing vinyl monomers and salts thereof, hydroxylgroup-containing vinyl monomers, and nitrogen-containing vinyl monomersare preferably used, more preferably, vinyl hydrocarbons, carboxylgroup-containing vinyl monomers and salts thereof, and sulfonic acidgroup-containing vinyl monomers and salts thereof, even more preferablyaromatic vinyl-based hydrocarbons, carboxyl group-containing vinylmonomers and salts thereof, and sulfonic acid group-containing vinylmonomers and salts thereof.

Among vinyl resins, as polymers obtained by copolymerizing vinylmonomers (copolymers of vinylmonomers), polymers obtained bycopolymerizing two or more of the monomers mentioned in (1) to (10) inany ratio are used. Examples of such copolymers includestyrene-(meth)acrylate copolymer, styrene-butadiene copolymer,(meth)acrylic acid-(meth)acrylate copolymer, styrene-acrylonitrilecopolymer, styrene-maleic acid (anhydride) copolymer,styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylicacid-divinylbenzene copolymer, and styrene-styrenesulfonicacid-(meth)acrylate copolymer, and the like.

As polyesters, polycondensation products of polyols with polycarboxylicacids, acid anhydrides thereof or lower alkyl esters thereof (alkylgroups having 1 to 4 carbon atoms), and the like can be used.

In polycondensation reaction, a well-known polycondensation catalyst orthe like can be used.

As polyols, diols (11) and polyols (12) having 3 to 6 or more hydroxylgroups can be used.

As polycarboxylic acids, acid anhydrides thereof, and lower alkyl estersthereof, dicarboxylic acids (13), polycarboxylic acids (14) having 3 to4 or more carboxyl groups, acid anhydrides thereof, and lower alkylesters thereof can be used.

Examples of the diols (11) include alkylene glycols having 4 to 30carbon atoms (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propyleneglycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol,dodecanediol, tetradecanediol, neopentyl glycol, and2,2-diethyl-1,3-propanediol), alkylene ether glycols having a molecularweight of 50 to 10,000 (e.g., diethylene glycol, triethylene glycol,dipropylene glycol, polyethylene glycol, polypropylene glycol, andpolytetramethylene ether glycol), alicyclic diols having 6 to 24 carbonatoms (e.g., 1,4-cyclohexane dimethanol and hydrogenated bisphenol A),bisphenols having 15 to 30 carbon atoms (e.g., bisphenol A, bisphenol F,and bisphenol S), polyphenols having 12 to 24 carbon atoms (e.g.,catechol, hydroquinone, and resorcin), alkylene oxides (hereinafter,simply referred to as “AO”) [e.g., ethylene oxide, propylene oxide, andbutylene oxide (hereinafter, simply referred to as “EO”, “PO”, and “BO”,respectively)] (2 to 100 mol) adducts of the above-mentioned alicyclicdiols having a molecular weight of 100 to 10,000 (e.g., EO (10 mol)adduct of 1,4-cyclohexane dimethanol), AO (EO, PO, or BO) (2 to 100 mol)adducts of the above-mentioned bisphenols (e.g., EO (2 mol) adduct ofbisphenol A, EO (4 mol) adduct of bisphenol A, PO (2 mol) adduct ofbisphenol A, PO (3 mol) adduct of bisphenol A, and PO (4 mol) adduct ofbisphenol A), polylactonediols having a weight average molecular weightof 100 to 5,000 (e.g., poly-ε-caprolactonediol), polybutadienediolhaving a weight average molecular weight of 1,000 to 20,000, and thelike.

Among these diols, alkylene glycols and AO adducts of bisphenols arepreferably used, more preferably AO adducts of bisphenols and mixturesof AO adducts of bisphenols and alkylene glycols.

Examples of the polyols (12) having 3 to 6 or more hydroxyl groupsinclude tri- to octa- or more polyhydric aliphatic alcohols having 3 to8 carbon atoms (e.g., glycerin, trimethylolethane, trimethylolpropane,pentaerythritol, sorbitan, and sorbitol), trisphenols having 25 to 50carbon atoms (e.g., trisphenol PA), novolac resins having a degree ofpolymerization of 3 to 50 (e.g., phenol novolac and cresol novolac),polyphenols having 6 to 30 carbon atoms (e.g., pyrogallol,phloroglucinol, and 1,2,4-benzenetriol), alkylene (having 2 to 4 carbonatoms) oxide (2 to 100 mol) adducts of the trisphenols mentioned above(e.g., EO (2 mol) adduct of trisphenol PA, EO (4 mol) adduct oftrisphenol PA, PO (2 mol) adduct of trisphenol PA, PO (3 mol) adduct oftrisphenol A, and PO (4 mol) adduct of trisphenol PA), alkylene (having2 to 4 carbon atoms) oxide (2 to 100 mol) adducts of the novolac resinsmentioned above (e.g., PO (2 mol) adduct of phenol novolac and EO (4mol) adduct of phenol novolac), alkylene (having 2 to 4 carbon atoms)oxide (2 to 100 mol) adducts of the polyphenols mentioned above (e.g.,EO (4 mol) adduct of pyrogallol), and acrylic polyols having a degree ofpolymerization of 20 to 2,000 (e.g., copolymers ofhydroxyethyl(meth)acrylate with other vinyl monomers such as styrene,(meth)acrylic acid, and (meth)acrylate), and the like.

Among these polyols, polyhydric aliphatic alcohols and AO adducts ofnovolac resins are preferably used, more preferably AO adducts ofnovolac resins.

Examples of the dicarboxylic acids (13) include alkanedicarboxylic acidshaving 4 to 32 carbon atoms (e.g., succinic acid, adipic acid, sebacicacid, dodecenylsuccinic acid, azelaic acid, dodecanedicarboxylic acid,and octadecanedicarboxylic acid), alkenedicarboxylic acids having 4 to32 carbon atoms (e.g., maleic acid, fumaric acid, citraconic acid, andmesaconic acid), branched-chain alkenedicarboxylic acids having 8 to 40carbon atoms (e.g., dimer acid and alkenylsuccinic acids such asdodecenylsuccinic acid, pentadecenylsuccinic acid, andoctadecenylsuccinic acid), branched-chain alkanedicarboxylic acidshaving 12 to 40 carbon atoms (e.g., alkylsuccinic acids such asdecylsuccinic acid, dodecylsuccinic acid, and octadecylsuccinic acid),and aromatic dicarboxylic acids having 8 to 20 carbon atoms (e.g.,phthalic acid, isophthalic acid, terephthalic acid, andnaphthalenedicarboxylic acid), and the like.

Among these dicarboxylic acids (13), alkenedicarboxylic acids andaromatic dicarboxylic acids are preferably used, more preferablyaromatic dicarboxylic acids.

Examples of the polycarboxylic acids (14) having 3 to 4 or more carboxylgroups include aromatic polycarboxylic acids having 9 to 20 carbonatoms, such as trimellitic acid, and pyromellitic acid, and the like.

Examples of acid anhydrides of the dicarboxylic acids (13) and thepolycarboxylic acids (14) having 3 to 4 or more carboxyl groups includetrimellitic anhydride and pyromellitic anhydride. Examples of loweralkyl esters thereof include methyl esters, ethyl esters, and isopropylesters.

In forming the polyester to be used in the present invention, the diols,the polyols having 3 to 6 or more hydroxyl groups, the dicarboxylicacids, the polycarboxylic acids having 3 to 4 or more carboxyl groups,and mixtures of two or more of them can be used in any ratio. Theequivalent ratio of hydroxyl group [OH] to carboxyl group [COOH], thatis, [OH]/[COOH] is preferably in the range of 2/1 to 1/1, morepreferably in the range of 1.5/1 to 1/1, even more preferably in therange of 1.3/1 to 1.02/1.

Further, the ester equivalent (that is, a molecular weight per oneequivalent of ester group) in the polyester is preferably in the rangeof 50 to 2,000, more preferably in the range of 60 to 1,000, even morepreferably in the range of 70 to 500.

As polyurethanes, polyaddition products of polyisocyanates (15) andactive hydrogen-containing compounds (β1) (e.g., water, the diols (11),the polyols (12) having 3 to 6 or more hydroxyl groups, the dicarboxylicacids (13), the polycarboxyic acids (14) having 3 to 4 or more carboxylgroups, polyamines (16), and polythiols (17)), and the like can be used.

In polyaddition reaction, a well-known polyaddition reaction catalyst orthe like can be used.

Examples of the polyisocyanates (15) include aromatic polyisocyanateshaving 6 to 20 carbon atoms (exclusive of the carbon in an NCO group;the same applies to the following description), aliphaticpolyisocyanates having 2 to 18 carbon atoms, alicyclic polyisocyanateshaving 4 to 15 carbon atoms, araliphatic polyisocynates having 8 to 15carbon atoms, and modification products of these polyisocyanates (e.g.,modified polyisocyanates having urethane, carbodiimide, allophanate,urea, biuret, urethodione, urethoimine, isocyanurate, or oxazolidonegroups), mixtures of two or more of them, and the like.

Examples of the aromatic polyisocyanates include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′-or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [phosgenide ofcrude diaminophenylmethane [a condensation product of formaldehyde witharomatic amine (aniline) or a mixture containing such aromatic amine; amixture of diaminodiphenylmethane and a small amount (e.g., 5 to 20%) ofpolyamine having 3 or more amino groups]: polyallyl polyisocyanate(PAPI)], 1,5-naphthylene diisocyante, 4,4′,4″-triphenylmethanetriisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, mixtures oftwo or more of them, and the like. It should be noted that all “%” inthis specification are by weight, unless otherwise specified.

Examples of the aliphatic polyisocyanates include ethylene diisocyanate,tetramethylene diisocyanate, hexamethylenediisocyanate (HDI),dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate,2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate,2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate,bis(2-isocyanatoethyl)carbonate,2-isocyanatoethyl-2,6-diisocyanatohexanoate, mixtures of two or more ofthem, and the like.

Examples of the alicyclic polyisocyanates include isophoronediisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenatedMDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate(hydrogenated TDI),bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- or2,6-norbornane diisocyanate, mixtures of two or more of them, and thelike.

Examples of the araliphatic polyisocyanates include m- or p-xylylenediisocyanate (XDI), α,α,α′,α′-tetramethylxylylene diisocyanate (TMXDI),mixtures of two or more of them, and the like.

Examples of the modification products of polyisocyanates includemodified polyisocyanates having urethane, carbodiimide, allophanate,urea, biuret, urethodione, urethoimine, isocyanurate and/or oxazolidonegroups, such as modified MDI (e.g., urethane-modified MDI,carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI),urethane-modified TDI, mixtures of two or more of them [e.g., a mixtureof the modified MDI and the urethane-modified TDI (isocyanate-containingprepolymer)], and the like.

Among these polyisocyanates, aromatic polyisocyanates, aliphaticpolyisocyanates, and alicyclic polyisocyanates are preferably used, morepreferably TDI, MDI, HDI, hydrogenated MDI, and IPDI.

As polyamines (16), aliphatic polyamines having 2 to 18 carbon atoms,aromatic polyamines having 6 to 20 carbon atoms, and the like can beused.

As aliphatic polyamines having 2 to 18 carbon atoms, (1) aliphaticpolyamines, (2) alkyl (having 1 to 4 carbon atoms)- or hydroxyalkyl(having 2 to 4 carbon atoms)-substituted aliphatic polyamines mentionedabove, (3) alicyclic or heterocycle-containing aliphatic polyamines, (4)aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms,and the like can be used.

(1) Examples of the aliphatic polyamines include alkylenediamines having2 to 12 carbon atoms (e.g., ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, and hexamethylenediamine),polyalkylene (having 2 to 6 carbon atoms) polyamines [e.g.,diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine,triethylenetetramine, tetraethylenepentamine, andpentaethylenehexamine], and the like.

(2) Examples of the alkyl (having 1 to 4 carbon atoms)- or hydroxyalkyl(having 2 to 4 carbon atoms)-substituted aliphatic polyamines mentionedabove include dialkyl (having 1 to 3 carbon atoms) aminopropylamine,trimethylhexamethylenediamine, aminoethylethanolamine,2,5-dimethyl-2,5-hexamethylenediamine, and methyliminobispropylamine,and the like.

(3) Examples of the alicyclic or heterocycle-containing aliphaticpolyamines include alicyclic polyamines having 4 to 15 carbon atoms{e.g., 1,3-diaminocyclohexane, isophoronediamine, menthenediamine,4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline),and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane}, andheterocyclic polyamines having 4 to 15 carbon atoms [e.g., piperazine,N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, and1,4-bis(2-amino-2-methylpropyl)piperazine], and the like.

(4) Examples of the aromatic ring-containing aliphatic amines (having 8to 15 carbon atoms) include xylylenediamine,tetrachloro-p-xylylenediamine, and the like.

As the above-mentioned aromatic polyamines having 6 to 20 carbon atoms,(1) unsubstituted aromatic polyamines, (2) aromatic polyamines nuclearlysubstituted by one or more alkyl groups (having 1 to 4 carbon atoms,such as methyl, ethyl, n- or i-propyl and butyl), (3) aromaticpolyamines having one or more electron-attracting groups such as halogen(e.g., Cl, Br, I, and F), alkoxy groups (e.g., methoxy and ethoxy), anda nitro group as nuclear substituents, and (4) secondary aminogroup-containing aromatic polyamines, and the like can be used.

(1) Examples of the unsubstituted aromatic polyamines include 1,2-, 1,3-or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, crudediphenylmethanediamine (polyphenylpolymethylenepolyamine),diaminodiphenyl sulfone, benzidine, thiodianiline,bis(3,4-diaminophenyl)sulfone, 2,6-diaminopyridine, m-aminobenzylamine,triphenylmethane-4,4′,4″-triamine, naphthylenediamine, mixtures of twoor more of them, and the like.

(2) Examples of the aromatic polyamines nuclearly substituted by one ormore alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-or i-propyl and butyl include 2,4- or 2,6-tolylenediamine, crudetolylenediamine, diethyltolylenediamine,4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis(o-toluidine),dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene,1,3-diethyl-2,4-diaminobenzene, 1,3-dimetnyl-2,6-diaminobenzene,1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene,1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene,1,3,5-triethyl-2,4-diaminobenzene,1,3,5-triisopropyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,6-diaminobenzene,2,3-dimethyl-1,4-diaminonaphthalene,2,6-dimethyl-1,5-diaminonaphthalene,2,6-diisopropyl-1,5-diaminonaphthalene,2,6-dibutyl-1,5-diaminonaphthalene, 3,3′5,5′-tetramethylbenzidine,3,3′,5,5′-tetraisopropylbenzidine,3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetrabutyl-4,4′-diaminodiphenylmethane,3,5-diethyl-3′-methyl-2′,4-diaminodiphenylmethane,3,5-diisopropyl-3′-methyl-2′,4-diaminodiphenylmethane,3,3′-diethyl-2,2′-diaminodiphenylmethane,4,4′-diamino-3,3′-dimethyldiphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diaminobenzophenone,3,3′,5,5′-tetraisopropyl-4,4′-diaminobenzophenone,3,3′,5,5′-tetraethyl-4,4′-diaminodiphenyl ether,3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenyl sulfone, mixtures of twoor more of them, and the like.

(3) Examples of the aromatic polyamines having one or moreelectron-attracting groups such as halogen (e.g., a chlorine atom, abromine atom, an iodine atom, and a fluorine atom), alkoxy groups (e.g.,methoxy and ethoxy), and a nitro group as nuclear substituents includemethylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine,2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline,4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine,5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline,4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane,3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine,bis(4-amino-3-chlorophenyl)oxide, bis(4-amino-2-chlorophenyl)propane,bis(4-amino-2-chlorophenyl)sulfone, bis(4-amino-3-methoxyphenyl)decane,bis(4-aminophenyl)sulfide, bis(4-aminophenyl)telluride,bis(4-aminophenyl)selenide, bis(4-amino-3-methoxyphenyl)disulfide,4,4′-methylenebis(2-iodoaniline), 4,4′-methylenebis(2-bromoaniline),4,4′-methylenebis(2-fluoroaniline), 4-aminophenyl-2-chloroaniline, andthe like.

(4) Examples of the secondary amino group-containing aromatic polyaminesinclude: aromatic polyamines obtained by replacing some or all of —NH₂groups in the aromatic polyamines (1) to (3) with —NH—R′ groups (whereinR′ represents an alkyl group such as a lower alkyl group having 1 to 4carbon atoms e.g., methyl, ethyl, or the like), such as4,4′-di(methylamino)diphenylmethane, and1-methyl-2-methylamino-4-aminobenzene, and the like; polyamidepolyamines such as low molecular-weight polyamide polyamines obtained bycondensation of dicarboxylic acids (e.g., dimer acid) with excess (thatis, 2 or more mols per mol of the acid) polyamines (e.g., thealkylenediamines and the polyalkylenepolyamines mentioned above);polyether polyamines such as hydrides of cyanoethylation products ofpolyether polyols (e.g., polyalkylene glycol); and the like.

As polythiols (17), dithiols having 2 to 24 carbon atoms, tri- to hexa-or higher valent polythiols having 5 to 30 carbon atoms, and the likecan be used.

Examples of dithiols include ethylenedithiol, 1,4-butanedithiol,1,6-hexanedithiol, and the like.

Examples of polythiols include Capcure-3800 (manufactured by Japan EpoxyResins Co., Ltd.), polyvinylthiol, and the like.

Among these active hydrogen-containing compounds (β1), water, the diols(11), the polyols (12), the dicarboxylic acids (13), and the polyamines(16) are preferably used, more preferably water, the diols (11), thepolyols (12), and the polyamines (16), even more preferably the diols(11), the polyols (12), and the polyamines (16).

As epoxy resins, ring-opening polymerization products of polyepoxides(18), polyaddition products of the polyepoxides (18) and the activehydrogen-containing compounds (β1), and curing reaction products of thepolyepoxides (18) and acid anhydrides of the dicarboxylic acids (13) orthe polycarboxylic acids (14) having 3 to 4 or more carboxyl groups, andthe like can be used.

In ring-opening polymerization reaction, polyaddition reaction, andcuring reaction, a well-known catalyst or the like can be used.

The polyepoxide (18) is not limited to any specific one as long as ithas two or more epoxy groups in the molecule, but from the viewpoint ofmechanical characteristics of the cured product, it preferably has 2 to6 epoxy groups in the molecule.

The epoxy equivalent (that is, molecular weight per epoxy group) of thepolyepoxide (18) is preferably in the range of 65 to 1,000. The upperlimit is more preferably 500, even more preferably 300. The lower limitis more preferably 70, even more preferably 90. If the epoxy equivalentexceeds the above upper limit, the cross-linked structure tends to beloose, thus resulting in lowering of physical properties of the curedproduct, such as water resistance, chemical resistance, mechanicalstrength, and the like. On the other hand, it is difficult to get (orsynthesize) polyepoxides having an epoxy equivalent less than the abovelower limit.

As polyepoxides (18), aromatic polyepoxides, heterocycle-containingpolyepoxides, alicyclic polyepoxides, aliphatic polyepoxides, and thelike can be used.

As aromatic polyepoxides, glycidyl ethers of polyhydric phenols,glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, andglycidylation products of aminophenols, and the like can be used.

Examples of the glycidyl ethers of polyhydric phenols include bisphenolF diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidylether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether,bisphenol A diglycidyl halides, tetrachlorobisphenol A diglycidyl ether,catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinonediglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether,octachloro-4,4′-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyldiglycidyl ether, dihydroxynaphthylcresol triglycidyl ether,tris(hydroxyphenyl)methanetriglycidyl ether, dinaphthyltriol triglycidylether, tetrakis(4-hydroxyphenyl)ethane tetraglycidyl ether,p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether,trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether,9,9′-bis(4-hydroxyphenyl)fluorene diglycidyl ether,4,4′-oxybis(1,4-phenylethyl)tetracresol glycidyl ether,4,4′-oxybis(1,4-phenylethyl)phenyl glycidyl ether,bis(dihydroxynaphthalene)tetraglycidyl ether, glycidyl ether of phenolor cresol novolac resin, glycidyl ether of limonene phenol novolacresin, diglycidyl ether obtained by the reaction between 2 mols ofbisphenol A and 3 mols of epichlorohydrin, polyglycidyl ethers ofpolyphenols obtained by condensation reaction of phenol with glyoxal,glutaraldehyde, or formaldehyde, polyglycidyl ether of polyphenolobtained by condensation reaction of resorcin with acetone, and thelike.

Examples of the glycidyl esters of polyhydric phenols include diglycidylphthalate, diglycidyl isophthalate, diglycidyl terephthalate, and thelike.

Examples of the glycidyl aromatic polyamines includeN,N-diglycidylaniline, N,N,N′,N′-tetraglycidylxylylenediamine, andN,N,N′,N′-tetraglycidyldiphenylmethanediamine, and the like.

Further, the epoxides include: triglycidyl ether of p-aminophenol;diglycidyl urethane compounds obtained by the addition reaction oftolylene diisocyanate or diphenylmethane diisocyanate and glycidol; anddiglycidyl ethers of AO (EO or PO) (2 to 20 mol) adducts of bisphenol A(e.g., diglycidyl ether of EO (4 mol) adduct of bisphenol A).

As heterocyclic polyepoxides, trisglycidylmelamine can be used.

As alicyclic polyepoxides, vinylcyclohexene dioxide, limonene dioxide,dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, ethyleneglycol bisepoxydicyclopentyl ether,3,4-epoxy-6-methylcyclohexylmethyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate,bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine, dimer acid diglycidylester, and nuclear hydrogenation products of aromatic polyepoxides(e.g., hydrogenated bisphenol F diglycidyl ether and hydrogenatedbisphenol A diglycidyl ether) can be used, for example.

As aliphatic polyepoxides, polyglycidyl ethers of polyhydric aliphaticalcohols, polyglycidyl esters of polyvalent fatty acids, glycidylaliphatic amines, and the like can be used.

Examples of the polyglycidyl ethers of polyhydric aliphatic alcoholsinclude ethylene glycol diglycidyl ether, propylene glycol diglycidylether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidylether, polyethylene glycol diglycidyl ether, polypropylene glycoldiglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerolpolyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitolpolyglycidyl ether, polyglycerol polyglycidyl ether, and the like.

Examples of the polyglycidyl esters of polyvalent fatty acids includediglycidyl oxalate, diglycidyl maleate, diglycidyl succinate, diglycidylglutarate, diglycidyl adipate, diglycidyl pimelate, and the like.

Examples of the glycidyl aliphatic amines includeN,N,N′,N′-tetraglycidyl hexamethylenediamine, andN,N,N′,N′-tetraglycidyl ethylenediamine, and the like.

The aliphatic polyepoxides include (co)polymers of diglycidyl ethers andglycidyl(meth)acrylates.

Among these polyepoxides, aliphatic polyepoxy compounds and aromaticpolyepoxy compounds are preferably used. In the present invention, thepolyepoxides may be used in combination of two or more of them.

The resin (a) constitutes a resin particle (B). The number averagemolecular weight (Mn), Tg, melting point, and SP value of the resin (a)can be appropriately adjusted to a value within a preferred rangeaccording to the purpose of use of the resin particles (B).

For example, in a case where the resin particles (B) are to be used as aresin for slush molding or a powder coating material, the Mn of theresin (a) is preferably in the range of 2,000 to 500,000, morepreferably in the range of 2,500 to 200,000, even more preferably in therange of 4,000 to 100,000.

In this regard, it should be noted that the number average molecularweights (Mn) and weight average molecular weights (Mw) in thisspecification were measured by gel permeation chromatography (GPC)(using a THF solvent and polystyrene as a standard substance).

Further, in a case where the resin (a) has a melting point, the meltingpoint of the resin (a) is preferably in the range of 0 to 250° C., morepreferably in the range of 35 to 200° C., even more preferably in therange of 40 to 180° C.

In this regard, it should be noted that the melting points in thisspecification were measured by DSC (differential scanning calorimeter)at a temperature rising rate of 20° C./min.

Furthermore, the Tg of the resin (a) is preferably in the range of −60to 100° C., more preferably in the range of −40 to 80° C., even morepreferably in the range of −30 to 70° C.

In this regard, it should be noted that the values of Tg in thisspecification were determined by DSC.

Moreover, the SP value of the resin (a) is preferably in the range of 7to 18, more preferably in the range of 8 to 16, even more preferably inthe range of 9 to 14.

In this regard, it should be noted that the SP values were calculatedaccording to a method described in Polymer Engineering and Science,February 1974, Vol. 14, No. 2, pp. 147 to 154.

In a case where the resin particles (B) are to be used as a spacer foruse in manufacturing electronic components or devices such as liquidcrystal displays or as standard particles for electronic measuringinstruments, the Mn of the resin (a) is preferably in the range of10,000 to 10,000,000, more preferably in the range of 15,000 to2,000,000, even more preferably in the range of 20,000 to 1,000,000.

Further, in a case where the resin (a) has a melting point, the meltingpoint of the resin (a) is preferably in the range of 50 to 300° C., morepreferably in the range of 80 to 250° C., even more preferably in therange of 100 to 240° C.

Furthermore, the Tg of the resin (a) is preferably in the range of 0 to250° C., more preferably in the range of 20 to 200° C., even morepreferably in the range of 35 to 150° C.

Moreover, the SP value of the resin (a) is preferably in the range of 8to 18, more preferably in the range of 9 to 16, even more preferably inthe range of 9.5 to 14.

In a case where the resin particles (B) are to be used as a toner forelectrophotography, electrostatic recording, or electrostatic printing,the Mn of the resin (a) is preferably in the range of 1,000 to5,000,000, more preferably in the range of 2,000 to 500,000, even morepreferably in the range of 3,000 to 100,000.

Further, in a case where the resin (a) has a melting point, the meltingpoint of the resin (a) is preferably in the range of 20 to 200° C., morepreferably in the range of 30 to 90° C., even more preferably in therange of 40 to 80° C.

Furthermore, the Tg of the resin (a) is preferably in the range of 20 to200° C., more preferably in the range of 30 to 90° C., even morepreferably in the range of 40 to 80° C.

Moreover, the SP value of the resin (a) is preferably in the range of 8to 16, more preferably in the range of 8.5 to 16, even more preferablyin the range of 9 to 14.

The resin particle (A) may contain an additive (T) (e.g., variousadditives such as a filler, a colorant, a plasticizer, a releasingagent, a charge control agent, a UV absorbing agent, an antioxidant, ananti-static agent, a fire retardant, an antibacterial agent, and apreservative) in addition to the resin (a).

The amount of the additive (T) contained in the resin particle (A) canbe appropriately set according to the purpose of use thereof, but ispreferably in the range of 0.01 to 200%, more preferably in the range of0.1 to 150%, even more preferably in the range of 0.2 to 100% withrespect to the weight of the resin particle (A).

Examples of a filler to be added include silica, alumina, titaniumoxide, barium titanate, magnesium titanate, calcium titanate, strontiumtitanate, zinc oxide, tin oxide, silicas and, clay, talc, wollastonite,diatomite, chromium oxide, ceric oxide, chromic oxide, ceric oxide,colcothar, antimony trioxide, magnesium oxide, zirconium oxide, bariumsulfate, barium carbonate, calcium carbonate, silicon carbide, andsilicon nitride.

Examples of a colorant to be added include all the well-known dyes andpigments such as Carbon black, Nigrosine dyes, Iron black, Naphtholyellow S, Hansa yellow (10G, 5G and G), Cadmium yellow, Yellow colorediron oxide, Yellow ochre, Chrome yellow, Titanium yellow, Polyazoyellow, Oil yellow, Hansa yellow (GR, A, RN and R), Pigment yellow L,Benzidine yellow (G and GR), Permanent yellow (NCG), Vulcan fast yellow(5G and R), Tartrazine lake, Quinoline yellow lake, Anthracene yellowBGL, Isoindolinone yellow, Colcothar, Red lead, Orange lead, Cadmiumred, Cadmium mercury red, Antimony orange, Permanent red 4R, Para red,Fire red, Parachloroorthonitro aniline red, Lithol fast scarlet G,Brilliant fast scarlet, Brilliant carmine BS, Permanent red (F2R, F4R,FRL, FRLL and F4RH), Fast scarlet VD, Vulcan fast rubine B, Brilliantscarlet G, Lithol rubine GX, Permanent red F5R, Brilliant carmine 6B,Pigment scarlet 3B, Bordeaux 5B, Toluidine maroon, Permanent bordeauxF2K, Helio bordeaux BL, Bordeaux 10B, BON maroon light, BON maroonmedium, Eosine lake, Rhodamine lake B, Rhodamine lake Y, Alizarin lake,Thioindigo red B, Thioindigo maroon, Oil red, Quinacridone red,Pyrazolone red, Polyazo red, Chrome vermilion, Benzidine orange,Perynone orange, Oil orange, Cobalt blue, Cerulean blue, Alkali bluelake, Peacock blue lake, Victoria blue lake, metal-free Phthalocyanineblue, Phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC),Indigo, Ultramarine, Prussian blue, Anthraquinone blue, Fast violet B,Methyl violet lake, Cobalt violet, Manganese violet, Dioxane violet,Anthraquinone violet, Chrome green, Zinc green, Chromium oxide,Viridian, Emerald green, Pigment green B, Naphthol green B, Green gold,Acid green lake, Malachite green lake, Phthalocyanine green,Anthraquinone green, Titanium oxide, Hydrozincite, Lithopone, andmixtures of two or more of them.

Examples of a plasticizer (L) to be added include, but not limited to,the following (L1) to (L5) and mixtures of two or more of them:

-   -   (L1) phthalic acid esters having 8 to 60 carbon atoms (e.g.,        dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate,        and diisodecyl phthalate);    -   (L2) aliphatic dibasic acid esters having 6 to 60 carbon atoms        (e.g., di-2-ethylhexyl adipate and 2-ethylhexyl sebacate);    -   (L3) trimellitic acid esters having 10 to 70 carbon atoms (e.g.,        tri-2-ethylhexyl trimellitate and trioctyl trimellitate);    -   (L4) phosphoric acid esters having 6 to 60 carbon atoms (e.g.,        triethyl phosphate, tri-2-ethylhexyl phosphate, and tricresyl        phosphate); and    -   (L5) fatty acid esters having 8 to 50 carbon atoms (e.g., butyl        oleate).

Among these plasticizers, (L1), (L2), (L3), and (L4) are preferablyused, more preferably (L1), (L2), and (L4), even more preferably (L1)and (L4).

As a releasing agent, waxes and silicone oils having a kinematicviscosity of 30 to 100,000 cSt at 25° C., and the like can be used.

Examples of a wax to be added include well-known waxes such aspolyolefin waxes (e.g., polyethylene wax and polypropylene wax),long-chain hydrocarbon waxes (e.g., paraffin wax and Sasol wax), andcarbonyl group-containing waxes. Among these waxes, carbonylgroup-containing waxes are preferably used. Examples of the carbonylgroup-containing wax include polyalkanoic acid esters (e.g., carnaubawax, montan wax, trimethylolpropane tribehenate, pentaerythritoltetrabehenate, pentaerythritol diacetate dibehenate, glycerintribehenate, and 1,18-octadecanediol distearate), polyalkanol esters(e.g., tristearyl trimellitate and distearyl maleate), polyalkanoic acidamides (e.g., ethylenediamine dibehenyl amide), polyalkylamides (e.g.,tristearylamide trimellitate), and dialkyl ketones (e.g., distearylketone). Among these carbonyl group-containing waxes, polyalkanoic acidesters are preferably used.

Examples of a charge control agent to be added include all thewell-known charge control agents such as nigrosine-based dyes,triphenylmethane-based dyes, chromium-containing metal complex dyes,molybdic acid chelate pigments, rhodamine-based dyes, alkoxy-basedamines, quaternary ammonium salts (including fluorine-modifiedquaternary ammonium salts), alkylamides, phosphorus or phosphoruscompounds, tungsten or tungsten compounds, fluorine-based activators,metal salts of salicylic acid, and metal salts of salicylic acidderivatives. Specific examples of the charge control agents includeBontron 03 as a nigrosine-based dye, Bontron P-51 as a quaternaryammonium salt, Bontron S-34 as a metal-containing azo dye, E-82 as anoxynaphthoic acid-based metal complex, E-84 as a salicylic acid-basedmetal complex, E-89 as a phenol-based condensation product, which aremanufactured by Orient Chemical Industries, Ltd.; TP-302 and TP-415 asquaternary ammonium salt molybdenum complexes, which are manufactured byHodogaya Chemical Co., Ltd.; Copy Charge PSY VP2038 as a quaternaryammonium salt, Copy blue PR as a triphenylmethane derivative, CopyCharge NEG VP2036 and Copy Charge NX VP434 as quaternary ammonium salts,which are manufactured by Hoechst; LRA-901 and LR-147 as a boroncomplex, which are manufactured by Japan Carlit Co., Ltd.; copperphthalocyanine, perylene, quinacridone, azo-based pigments, and otherpolymeric compounds having a functional group such as a sulfo group, acarboxyl group, or a quaternary ammonium salt group.

A method for adding the additive (T) to the resin particles (A) is notlimited to any specific one. For example, in the preparing method ofresin particles according to the present invention (which will bedescribed later), the additive (T) may be added to an aqueous medium, ora mixture of the resin (a) and the additive (T) may be dispersed in anaqueous medium.

In this regard, it is to be noted that it is not always necessary to addthe additive (T) in course of the formation of the resin particles (A),and the additive (T) may be added after the formation of the resinparticles (A). For example, a colorant may be added in accordance with awell-known dyeing method after the formation of the resin particles (A)containing no colorant, or the resin particles (A) may be impregnatedwith the additive (T) together with a solvent (U) (which will bedescribed later) and/or the plasticizer (L).

In a case where a colorant is added to the resin particles (A) as anadditive, the colorant may be one treated with a coupling agent such asa silane coupling agent, a titanium coupling agent, an aluminum couplingagent, or the like.

Particularly, in a case where carbon black is used as a colorant, carbonblack treated with an aluminum coupling agent is preferably used.

As a method for allowing the resin particles (A) to contain a coloranttreated with a coupling agent, a method in which a dispersion liquidcontaining a colorant treated with an aluminum coupling agent is formedto mix it with the resin (a) can be mentioned, for example.

In the formation of a dispersion liquid containing a colorant, it ispreferred that the colorant and an aluminum coupling agent are firstmixed by a wet method. Mixing of a colorant and an aluminum couplingagent is carried out using an ordinary mixer or agitator. Specifically,a colorant and an aluminum coupling agent are placed in an appropriatecontainer equipped with particulate media such as an Atliter, a ballmill, a sand mill, a vibration mill, or the like, and then they areagitated. Preferred examples of particulate media to be used includesteel such as stainless steel and carbon steel, alumina, zirconia, andsilica, and the like. In the process, a temperature within the containeris kept at 20 to 160° C., preferably at 20 to 100° C., more preferablyat 30 to 60° C. By using such an agitator, it is possible to release thecolorant from agglomeration and to disperse the colorant so that theaverage particle size of the colorant becomes about 0.7 μm or less,preferably about 0.4 μm or less and, further, to apply load so that thealuminum coupling agent is made to react with and adsorbed to thecolorant. Next, it is preferred that the colorant dispersion liquid isagain dispersed by high speed shearing or the like in order to preventagglomeration of the colorant in the mixing of the colorant dispersionliquid with the binder resin. Dispersion can be carried out by adispersing machine having a high-speed blade rotation type or forcedgap-passing type high-speed shearing system, such as various homomixers,homogenizers, colloid mills, Ultra-Turrax, Clear Mill, or the like.

The aluminum coupling agent to be used is not limited to any specificone as long as it is a compound capable of coupling with a colorant.Examples of such an aluminum coupling agent include alkyl (having 1 to30 carbon atoms) acetoacetate aluminum isopropylate, aluminum tris(ethylacetoacetate), and aluminum monoisopropoxy monooleoxy ethylacetoacetate.

The amount of the aluminum coupling agent to be used is preferably inthe range of 0.1 to 100 parts with respect to 100 parts of the colorantfrom the viewpoint of dispersibility of the colorant in the resin (a).The upper limit is more preferably 50 parts, even more preferably 30parts. The lower limit is more preferably 0.3 parts In this regard, itis to be noted that “parts” in this specification refers to parts byweight.

A method for preparing an aqueous dispersion (I) containing the resinparticles (A) is not limited to any specific one, but examples of such amethod include a method in which a precursor of the resin (a) is allowedto react in an aqueous medium, a method in which a dead polymer of theresin (a) is formed to disperse it in an aqueous medium, and a method inwhich a dead polymer of the resin (a) is dispersed in an aqueous medium,and a precursor of the resin (a) is allowed to react in the aqueousmedium.

Examples of a method, in which a precursor of the resin (a) is allowedto react in an aqueous medium, include the following methods (1) and(2):

-   -   (1) in a case where vinyl resins are concerned, a method in        which an aqueous dispersion of the resin particles (A) is        prepared using a monomer as an initial material under the        presence of polymerization catalyst by polymerization reaction        such as suspension polymerization, emulsion polymerization, seed        polymerization, or dispersion polymerization; and    -   (2) in a case where polyaddition or condensation resins such as        polyesters, polyurethanes, and epoxy resins are concerned, a        method in which a precursor (a0) of the resin (a) or a solvent        solution of the precursor (a0) is dispersed in an aqueous medium        under the presence of a suitable dispersant, and is then cured        by heating or adding a curing agent (which is a compound having        at least 2 functional groups capable of reacting with the        precursor in the molecule) to produce an aqueous dispersion of        the resin particles (A).

Examples of a method, in which a dead polymer of the resin (a) is formedto disperse it in an aqueous medium, include the following methods (3)to (7):

-   -   (3) a method in which the resin (a) produced in advance by        polymerization reaction (which may be carried out by any        polymerization reaction method such as addition polymerization,        ring-opening polymerization, polyaddition, addition        condensation, condensation polymerization, or the like) is        ground using a mechanical rotary or jet type pulverizer, and is        then classified to obtain resin particles (A), and the resin        particles (A) are dispersed in water under the presence of a        suitable dispersant;    -   (4) a method in which a solution of the resin (a) which is        produced in advance by polymerization reaction (which may be        carried out by any polymerization reaction method such as        addition polymerization, ring-opening polymerization,        polyaddition, addition condensation, condensation        polymerization, or the like) is sprayed in a mist form to obtain        resin particles (A) from which the solvent is removed, and the        resin particles (A) are dispersed in water under the presence of        a suitable dispersant;    -   (5) a method in which the resin (a) is in advance produced by        polymerization reaction (which may be carried out by any        polymerization reaction method such as addition polymerization,        ring-opening polymerization, polyaddition, addition        condensation, condensation polymerization, or the like), resin        particles are precipitated by adding a poor solvent (which is a        solvent incapable of dissolving the resin (a) in 1% or more at        25° C.) to a solution of the resin (a) or by cooling a solution        of the resin (a) produced in advance by dissolving the resin (a)        in a solvent by heating, the solvent is removed to obtain resin        particles (A), and the resin particles (A) are dispersed in        water under the presence of a suitable dispersant;    -   (6) a method in which a solution of the resin (a) which is        produced in advance by polymerization reaction (which may be        carried out by any polymerization reaction method such as        addition polymerization, ring-opening polymerization,        polyaddition, addition condensation, condensation        polymerization, or the like) is dispersed in an aqueous medium        under the presence of a suitable dispersant, and then the        solvent is removed by heating or decompression; and    -   (7) a method in which in a solution of the resin (a) which is        produced in advance by polymerization reaction (which may be        carried out by any polymerization reaction method such as        addition polymerization, ring-opening polymerization,        polyaddition, addition condensation, condensation        polymerization, or the like), a suitable emulsifier is        dissolved, then water is added for phase inversion        emulsification, and thereafter the solvent is removed by heating        or decompression.

Examples of a method, in which a dead polymer of the resin (a) isdispersed in an aqueous medium and then a precursor of the resin (a) isallowed to react in the aqueous medium, include a method in which aprecursor of the resin (a) is allowed to react by the method (2) in anaqueous medium, in which a dead polymer is dispersed, obtained by anyone of the methods (3) to (7) (e.g., a combination of the methods (6)and (2)). According to such a method, by selecting appropriateproduction conditions as described in, for example, PCT publication No.WO 01/60893, it is possible to obtain an aqueous dispersion (I) ofcomposite resin particles in which resin particles (A1) of a deadpolymer are attached to the surface of resin particles (A2) obtained byallowing a precursor to react. This method is preferred because a resindispersion having a uniform particle diameter can be obtained. In thisregard, it is to be noted that a resin (a2) obtained by allowing aprecursor to react and a dead polymer resin (a1) may be the same ordifferent from each other.

The particle diameter of the resin particles (A1) is smaller than thatof the resin particles (A2). From the viewpoint of particle sizeuniformity, the ratio between the volume average particle diameter ofthe resin particles (A1) (hereinafter, simply referred to as “DA1”) andthe volume average particle diameter of the resin particles (A2)(hereinafter, simply referred to as “DA2”) (that is, DA1/DA2) preferablylies in the range of 0.0001 to 0.5. The upper limit is more preferably0.4, even more preferably 0.3, the lower limit is more preferably0.0005, even more preferably 0.001. By setting DA1/DA2 to a value withinthe above range, it is possible to allow the resin particles (A1) toadsorb to the surface of the resin particles (A2) efficiently. Further,it is also possible to make the particle size distribution of thecomposite resin particles sharp.

Further, from the viewpoint of achieving an appropriate SF-1 of thecomposite resin particles and improving particle size uniformity and theviewpoint of storage stability of the composite resin particles, theamount of the resin particles (A1) with respect to the total weight ofthe resin particles (A1) and the resin particles (A2) in the compositeresin particles preferably lies in the range of 0.01 to 60%. The upperlimit is more preferably 55%, even more preferably 50%, the lower limitis more preferably 0.05%, even more preferably 0.01%.

In these producing methods of the aqueous dispersion (I), the solid(which is a component other than a solvent) concentration of the aqueousdispersion preferably lies in the range of 1 to 70%, more preferably inthe range of 5 to 65%, even more preferably in the range of 10 to 60%.

Among the above-described methods (1) to (7), the methods (1), (2), (6),and (7) and a combination of two or more of them are preferable, themethods (1), (2), and (6) and a combination of two or more of them aremore preferable, and the methods (2) and (6) and a combination of themare even more preferable.

The method in which a precursor of the resin (a) is allowed to react inan aqueous medium will be described in more detail.

The precursor (a0) of the resin (a) is not limited to any specific oneas long as it can be converted to the resin (a) by chemical reaction.For example, in a case where the resin (a) is a vinyl resin, examples ofthe precursor (a0) include the vinyl monomers mentioned above (which maybe used singly or in combination of two or more of them) and solutionsthereof.

In a case where the vinyl monomer is used as the precursor (a0),examples of the method for allowing the precursor (a0) to react toconvert it to the resin (a) include a method in which an oil phasecomprised of an oil-soluble initiator, the monomer and, as necessary, asolvent (U) (which will be described later) is dispersed and suspendedin water under the presence of a synthetic polymeric dispersant (H) tocarry out radical polymerization reaction by heating (that is, theso-called suspension polymerization method), and a method in which anoil phase comprised of the monomer and, as necessary, a solvent (U) isemulsified in water containing an emulsifier and a water-solubleinitiator to carry out radical polymerization reaction by heating (thatis, the so-called emulsion polymerization method).

As the oil-soluble initiator and the water-soluble initiator, peroxidepolymerization initiators, and azo polymerization initiators, and thelike can be used. A peroxide polymerization initiator may be used incombination with a reducing agent to form a redox polymerizationinitiator. Further, these initiators can be used in combination of twoor more of them.

Examples of the peroxide polymerization initiators include oil-solubleperoxide polymerization initiators and water-soluble peroxidepolymerization initiators. As oil-soluble peroxide polymerizationinitiators, acetylcyclohexylsulfonyl peroxide, isobutylyl peroxide,diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate,2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate,3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide,lauroyl peroxide, stearoly peroxide, propionitrile peroxide, succinicacid peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoylperoxide, p-chlorobenzoyl peroxide, t-butylperoxyisobutylate, t-butylperoxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide,t-butyl peroxyisopropylcarbonate,2,5-dimethyl-2,5-dibenzoylperoxyhexane, t-butyl peroxyacetate, t-butylperoxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketoneperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane,t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide,diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, pinanehydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide,and the like can be used. As water-soluble peroxide polymerizationinitiators, hydrogen peroxide, peracetic acid, ammonium persulfate,potassium persulfate, sodium persulfate, and the like can be used.

Examples of the azo polymerization initiators include oil-soluble azopolymerization initiators and water-soluble azo polymerizationinitiators. As oil-soluble azo polymerization initiators,2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane-1-carbonytrile,2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile,2,2′-azobis-2,4-dimethylvaleronitrile,dimethyl-2,2′-azobis(2-methylpropionate),1,1′-azobis(1-acetoxy-1-phenylethane),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like can beused. As water-soluble azo polymerization initiators,azobisamidinopropane salt, azobiscyanovaleric acid (salt),2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and the like canbe used.

As redox polymerization initiators, oil-soluble redox polymerizationinitiators and water-soluble redox polymerization initiators can bementioned.

Examples of the oil-soluble redox polymerization initiators includecombinations of oil-soluble peroxides such as hydroperoxides (e.g.,tert-butyl hydroxyperoxide and cumene hydroxyperoxide), dialkylperoxides (e.g., lauroyl peroxide), diacyl peroxides (e.g., benzoylperoxide), and the like and oil-soluble reducing agents such as tertiaryamines (e.g., triethylamine and tributylamine), naphthenic acid salts,mercaptans (e.g., mercaptoethanol and lauryl mercaptan), organic metalcompounds (e.g., triethylaluminum, triethylboron, and diethylzinc), andthe like.

Examples of the water-soluble redox polymerization initiators includecombinations of water-soluble peroxides such as persulfate salts (e.g.,potassium persulfate and ammonium persulfate), hydrogen peroxide,hydroperoxides (e.g., tert-butyl hydroxyperoxide and cumenehydroxyperoxide), and the like and water-soluble inorganic or organicreducing agents such as iron (II) salts, sodium bisulfite, alcohols, anddimethylaniline).

In a case where the resin (a) is a condensed resin (e.g., polyurethane,an epoxy resin, or polyester), a combination of a reactivegroup-containing prepolymer (α) (which will be described later) and acuring agent (β) may also be used as the precursor (a0) Here, the word“reactive group” means a group capable of reacting with the curing agent(β).

In this case, examples of a method of allowing the precursor (a0) toreact to form the resin particles (A) include the following methods (1)to (3):

-   -   (1) a method in which an oil phase containing the reactive        group-containing prepolymer (α), the curing agent (β) and, as        necessary, the solvent (U) is dispersed in an aqueous medium,        and then the reactive group-containing prepolymer (α) and the        curing agent (β) are allowed to react by heating to form the        resin particles (A) comprising the resin (a);    -   (2) a method in which the reactive group-containing prepolymer        (α) or a solution thereof is dispersed in an aqueous medium, and        a water-soluble curing agent (β) is added thereto to allow them        to react so as to form the resin particles (A) comprising the        resin (a); and    -   (3) a method in which the reactive group-containing prepolymer        (α) or a solution thereof is dispersed in an aqueous medium to        allow the reactive group-containing prepolymer (α) to react with        water to form the resin particles (A) comprising the resin (a),        the method being applicable to a case where the reactive        group-containing prepolymer (α) can be cured by the reaction        with water.

Examples of a combination of the reactive group contained in thereactive group-containing prepolymer (α) and the curing agent (β)include the following combinations (1) and (2):

-   -   (1) a combination of a reactive group-containing prepolymer (α1)        having a functional group capable of reacting with an active        hydrogen-containing group and an active hydrogen-containing        compound (β1) which may be blocked with a removal compound; and    -   (2) a combination of a reactive group-containing prepolymer (α2)        having an active hydrogen-containing group, and a curing agent        (β2) having a functional group capable of reacting with an        active hydrogen-containing group.

Among these combinations, the combination (1) is preferably used fromthe viewpoint of reaction rate in water.

Examples of a functional group capable of reacting with an activehydrogen-containing group include an isocyanate group, a blockedisosyanate group, an epoxy group, an acid anhydride group, and an acidhalide (e.g., acid chlorides and acid bromides) group.

Among them, an isocyanate group, a blocked isocyanate group, and anepoxy group are preferably used, more preferably an isocyanate group anda blocked isocyanate group.

In this regard, it is to be noted that the blocked isocyanate groupmeans an isocyanate group that is blocked with a blocking agent.

Examples of the blocking agent include well-known blocking agents suchas oximes (e.g., acetoxime, methyl isobutyl ketoxime, diethyl ketoxime,cyclopentanone oxime, cyclohexanone oxime and methyl ethyl ketoxime),lactams (e.g., γ-butyrolactam, ε-caprolactam, and γ-valerolactam),aliphatic alcohols having 1 to 20 carbon atoms (e.g., ethanol, methanol,and octanol), phenols (e.g., phenol, m-cresol, xylenol, andnonylphenol), active methylene compounds (e.g., acetylacetone, ethylmalonate, and ethyl acetoacetate), basic nitrogen-containing compounds(e.g., N,N-diethylhydroxylamine, 2-hydroxypiridine, pyridine N-oxide,and 2-mercaptopyridine), and mixtures of two or more of them.

Among these blocking agents, oximes are preferably used, more preferablymethyl ethyl ketoxime.

As the skeleton of the reactive group-containing prepolymer (α),polyethers, polyesters, epoxy resins, or polyurethanes can be used.

Among them, polyesters, epoxy resins, and polyurethanes are preferablyused, more preferably polyesters and polyurethanes.

Examples of polyethers include polyethylene oxide, polypropylene oxide,polybutylene oxide, and polytetramethylene oxide.

Examples of polyesters include polycondensation products of the diols(11) and the dicarboxylic acids (13), and polylactones (e.g., thering-opening polymerization product of ε-caprolactone).

Examples of epoxy resins include addition-condensation products ofbisphenols (e.g., bisphenol A, bisphenol F, and bisphenol S) andepichlorohydrine.

Examples of polyurethanes include polyaddition products of the diols(11) and the polyisocyanates (15), and polysddition products of thepolyesters and the polyisocyanates (15).

A method of introducing the above mentioned reactive group into thepolyester, the epoxy resin, or the polyurethane is not limited to anyspecific one, but examples of such a method include the followingmethods (1) and (2):

-   -   (1) a method in which one of components constituting the        polyester, the epoxy resin, or the polyurethane is used        excessively to allow a reactive group of the component to        remain; and    -   (2) a method in which one of components constituting the        polyester, the epoxy resin, or the polyurethane is used        excessively to allow a functional group of the component to        remain, and then the functional group is further reacted with a        compound having a functional group (reactive group) capable of        reacting with the remaining functional group.

According to the method (1), it is possible to obtain a hydroxylgroup-containing polyester prepolymer, a carboxyl group-containingpolyester prepolymer, an acid halide group-containing polyesterprepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxygroup-containing epoxy resin prepolymer, a hydroxyl group-containingpolyurethane prepolymer, and an isocyanate group-containing polyurethaneprepolymer, and the like.

For example, in the case of a hydroxyl group-containing polyesterprepolymer, the ratio between the components in the method (1), that is,the ratio between the alcohol components (e.g., the diols (11) and thepolyols (12)) and the carboxylic acid components (e.g., the dicarboxylicacids (13) and the polycarboxylic acids (14)) as expressed in terms ofthe equivalent ratio of hydroxyl group [OH] to carboxyl group [COOH],that is, the equivalent ratio [OH]/[COOH] is preferably in the range of2/1 to 1/1, more preferably in the range of 1.5/1 to 1/1, even morepreferably in the range of 1.3/1 to 1.02/1.

In each of the cases of a carboxyl group-containing polyesterprepolymer, an acid halide group-containing polyester prepolymer, ahydroxyl group-containing polyurethane prepolymer, and an isocyanategroup-containing polyurethane prepolymer, components thereof aredifferent from those of the example case, but a preferred ratio betweenthe components is the same as described above.

According to the method (2), an isocyanate group-containing prepolymercan be obtained by allowing a prepolymer obtained by the method (1) toreact with polyisocyanate, a blocked isocyanate group-containingprepolymer can be obtained by allowing a prepolymer obtained by themethod (1) to react with blocked polyisocyanate, an epoxygroup-containing prepolymer can be obtained by allowing a prepolymerobtained by the method (1) to react with polyepoxide, and an acidanhydride group-containing prepolymer can be obtained by allowing aprepolymer obtained by the method (1) to react with a compound having 2or more acid anhydride groups.

For example, in the case of obtaining an isocyanate group-containingpolyester prepolymer by allowing a hydroxyl group-containing polyesterto react with polyisocyanate according to the method (2), the amount ofthe compound having are active group to be used, that is, the ratiobetween the hydroxyl group-containing polyester and polyisocyanate to beused as expressed in terms of the equivalent ratio of isocyanate group[NCO]/hydroxyl group [OH], that is, the equivalent ratio [NCO]/[OH] ispreferably in the range of 5/1 to 1/1, more preferably in the range of4/1 to 1.2/1, even more oreferably in the range of 2.5/1 to 1.5/1.

In each of the cases of other prepolymers, components thereof aredifferent from those of the example case, but a preferred ratio betweenthe components is the same as described above.

The average number of the reactive group per molecule contained in thereactive group-containing prepolymer (α) is preferably in the range of 1to 3, more preferably in the range of 1.5 to 3, even more preferably inthe range of 1.8 to 2.5. By setting the average number of the reactivegroup per molecule contained in the reactive group-containing prepolymer(α) to a value within the above range, it is possible for the resin (a)obtained by the reaction with the curing agent (β) to have highmechanical strength.

The Mn of the reactive group-containing prepolymer (α) is preferably inthe range of 500 to 30,000. The upper limit is more preferably 20,000,even more 10,000, the lower limit is more preferably 1,000, even more2,000.

The Mw of the reactive group-containing prepolymer (α) is preferably inthe range of 1,000 to 50,000. The upper limit is more preferably 40,000,even more preferably 20,000, the lower limit is more preferably 2,000,even more preferably 4,000.

As the active hydrogen group-containing compounds (β1), polyamines whichmay be blocked with removable compounds and polyols which may be blockedwith removable compounds can be mentioned, in addition to the abovementioned water, the diols (11), the polyols (12) having 3 to 6 or morehydroxyl groups, the dicarboxylic acids (13), the polycarboxylic acids(14) having 3 to 4 or more carboxyl groups, the polyamines (16), and thepolythiols (17).

Examples of a polyamine blocked with a removable compound includeketimine compounds obtained by dehydration between the polyamines (16)and ketones having 3 to 8 carbon atoms (e.g., acetone, methyl ethylketone, and methyl isobutyl ketone), aldimine compounds obtained bydehydration between the polyamines (16) and aldehyde compounds having 2to 8 carbon atome (e.g., formaldehyde and acetaldehyde), enaminecompounds obtainable from the polyamines (16) and ketones having 3 to 8carbon atoms or aldehydes having 2 to 8 carbon atoms, and oxazolidinecompounds.

Among these active hydrogen group-containing compounds (β1), polyamineswhich may be blocked, polyols which may be blocked, and water arepreferably used, more preferably polyamines which may be blocked andwater, even more preferably polyamines, ketimine compounds and water,most preferably 4,4′-diaminodiphenylmethane, xylylenediamine,isophoronediamine, ethylenediamine, diethylenetriamine,triethylenetetramine, ketimine compounds obtainable from thesepolyamines and ketones, and water.

When the resin particles (A) are produced, a reaction terminator (βs)may be used as necessary together with the active hydrogengroup-containing compound (β1). By using the reaction terminator (βs)and the active hydrogen group-containing compound (β1) together in acertain ratio, it becomes easy to control the molecular weight of theresin (a) comprising the resin particles (A).

Examples of such a reaction terminator (βs) include monoamines having 1to 40 carbon atoms (e.g., diethylamine, dibutylamine, butylamine,laurylamine, monoethanolamine, and diethanolamine), blocked monoamineshaving 3 to 40 carbon atoms (e.g., ketimine compounds), monools having 1to 40 carbon atoms (e.g., methanol, ethanol, isopropanol, butanol, andphenol), monomercaptans having 2 to 40 carbon atoms (e.g.,butylmercaptan and laurylmercaptan), monoisocyanates having 5 to 40carbon atoms (e.g., butyl isocyanate, lauryl isocyanate, and phenylisocyanate), and monoepoxides having 2 to 40 carbon atoms (e.g., butylglycidyl ether).

In the combination (2) described above (that is, in the combination ofthe reactive group-containing prepolymer (α2) having an activehydrogen-containing group and the curing agent (β2) having a functionalgroup capable of reacting with an active hydrogen-containing group),examples of the active hydrogen-containing group contained in thereactive group-containing prepolymer (α) include an amino group,hydroxyl groups (an alcoholic hydroxyl group and a phenolic hydroxylgroup), a mercapto group, a carboxyl group, and organic groups obtainedby blocking these groups with removable compounds (e.g., ketones andaldehydes) (e.g., a ketimine-containing group, an aldimine-containinggroup, an oxazolidine-containing group, an enamine-containng group, anacetal-contianing group, a ketal-containing group, athioacetal-containing group, and a thioketal-containing group).

Among these active hydrogen-containing groups, an amino group, hydroxylgroups, and organic groups obtained by blocking these groups withremovable compounds are preferably used, more preferably hydroxylgroups.

Examples of the curing agent (β2) having a functional group capable ofreacting with an active hydrogen-containg group include thepolyisocyanates (15), the polyepoxides (18), the dicarboxylic acids(13), the polycarboxylic acids (14), compounds having two or more acidanhydride groups, and compounds having two or more acid halide groups.

Among these curing agents (β2), the polyisocyanates and the polyepoxidesare preferably used, more preferably the polyisocyanates.

Examples of the compound having two or more acid anhydride groupsinclude a (co)polymer of pyromellitic anhydride and polymaleicanhydride, and the like.

Examples of the compound having two or more acid halide groups includeacid halides (e.g., acid chloride, acid bromide, and acid iodide) of thedicarboxylic acids (13) or the polycarboxylic acids (14).

When the resin particles (A) are produced, the reaction terminator (βs)may be used as necessary together with the curing agent (β2) having afunctional group capable of reacting with an active hydrogen-containinggroup. By using the reaction terminator (βs) and the curing agent (β2)together in a certain ratio, it becomes easy to control the molecularweight of the resin (a) constituting the resin particles (A).

The amount of the curing agent (β) to be used as expressed in terms ofthe ratio [α]/[β] of the equivalent of the reactive group [α]in thereactive group-containing prepolymer (α) to the equivalent of the activehydrogen-containing group [β]in the curing agent (β) is preferably inthe range of 1/2 to 2/1, more preferably in the range of 1.5/1 to 1/1.5,even more preferably in the range of 1.2/1 to 1/1.2.

In a case where water is used as the curing agent (β), water isconsidered as a bifunctional active hydrogen-containing compound.

The length of time of reaction between the reactive group-containingprepolymer (α) and the curing agent (β) is selected according toreactivity that depends on the combination of the kind of reactive groupcontained in the prepolymer (α) and the curing agent (β), but ispreferably in the range of 10 minutes to 40 hours, more preferably inthe range of 30 minutes to 24 hours, even more preferably in the rangeof 30 minutes to 8 hours.

Further, the temperature of the reaction is preferably in the range of 0to 150° C., more preferably in the range of 50 to 120° C.

As necessary, a well-known catalyst can be used. Specifically, in thecase of the reaction between isocyanate and an activehydrogen-containing compound by way of example, dibutyltin laurate,dioctyltin laurate or the like can be used.

As the emulsifier and the dispersant used in the above-mentioned methods(1) to (7) for obtaining the aqueous dispersant (I), well-knownsurfactants (S) and synthetic polymeric dispersants (H), and the likecan be mentioned.

In a case where the surfactant (S) is used, the amount thereof to beused is preferably in the range of 0.0001 to 50%, more preferably in therange of 0.0.005 to 0.4%, even more preferably in the range of 0.001 to0.3% with respect to the weight of the resin (a) and the precursorthereof (a0).

In a case where the synthetic polymeric dispersant (H) is used, theamount thereof to be used is preferably in the range of 0.005 to 0.6%,more preferably in the range of 0.01 to 0.4%, even more preferably inthe range of 0.02 to 0.3% with respect to the weight of the resin (a)and the precursor thereof (a0).

Further, the plasticizer (L) or the like may be used as an emulsifierassistant or a dispersant assistant.

In a case where the plasticizer (L) is used, the amount thereof to beused is preferably in the range of 0.01 to 0.3%, more preferably in therange of 0.02 to 0.25%, even more preferably in the range of 0.03 to0.2% with respect to the weight of the resin (a) and the precursorthereof (a0).

The plasticizer (L) may be added as necessary to either water or theresin (a) at dispersion-emulsification.

As surfactants (S), anionic surfactants (S-1), cationic surfactants(S-2), amphoteric surfactants (S-3), and nonionic surfactants (S-4), andthe like can be used. In this regard, it is to be noted that thesesurfactants (S) can be used in combination of two or more of them.

Examples of the anionic surfactant (S-1) include carboxylic acids orsalts thereof, sulfuric acid ester salts, salts of carboxymethylationproducts, sulfonic acid salts, and phosphoric acid ester salts.

As carboxylic acids or salts thereof, saturated or unsaturated fattyacids having 8 to 22 carbon atoms or salts thereof can be used, andexamples of such carboxylic acids include capric acid, lauric acid,myristic acid, palmitic acid, stearic acid, arachidic acid, behenicacid, oleic acid, linoleic acid, ricinoleic acid, and mixtures of higherfatty acids obtained by saponifying coconut oil, palm kernel oil, ricebran oil, beef tallow, and the like.

As the salts of these carboxylic acids, sodium salts, potassium salts,amine salts, ammonium salts, quaternary ammonium salts, and alkanolaminesalts (e.g., monoethanolamine salt, diethanolamine salt, andtriethanolamine salt), and the like can be mentioned.

As sulfuric acid ester salts, higher alcohol sulfuric acid ester salts(C₈-C₁₈ aliphatic alcohol sulfuric acid ester salts), higher alkyl ethersulfuric acid ester salts (C₈-C₁₈ aliphatic alcohol-E or PO (1 to 10mol) adduct sulfuric acid ester salts), sulfated oils (which areobtained by directly sulfating and neutralizing naturally-occurringunsaturated fats and oils having 12 to 50 carbon atoms or unsaturatedwaxes), sulfated fatty acid esters (which are obtained by sulfating andneutralizing lower alcohol (having 1 to 8 carbon atoms) esters ofunsaturated fatty acids (having 6 to 40 carbon atoms)), and sulfatedolefins (which are obtained by sulfating and neutralizing olefins having12 to 18 carbon atoms), and the like can be used.

As the salts, sodium salts, potassium salts, amine salts, ammoniumsalts, quaternary ammonium salts, alkanolamine salts (e.g.,monoethanolamine salt, diethanolamine salt, and triethanolamine salt),and the like can be mentioned.

Examples of the higher alcohol sulfuric acid ester salts include saltsof octyl alcohol sulfate, salts of decyl alcohol sulfate, salts oflauryl alcohol sulfate, salts of stearyl alcohol sulfate, sulfuric acidester salts of alcohols synthesized using a Ziegler catalyst (e.g.,“ALFOL 1214” which is a product of CONDEA), and sulfuric acid estersalts of alcohols synthesized by oxo process (e.g., “Dobanol 23, 25, 45”and “Diadol 115-L, 115-H, 135” which are products of Mitsubishi ChemicalCorporation, “Tridecanol” which is a product of Kyowa Hakko Kogyo Co.,Ltd., and “Oxocol 1213, 1215, 1415” which are products of NissanChemical Industries, Ltd.).

Examples of the higher alkyl ether sulfuric acid ester salts includelauryl alcohol-EO (2 mol) adduct sulfuric acid ester salts, and octylalcohol-EO (3 mol) adduct sulfuric acid ester salts.

Examples of the sulfated oil include salts of sulfation products ofcastor oil, arachis oil, olive oil, rape oil, beef tallow, muttontallow, and the like.

Examples of the sulfated fatty acid ester include salts of sulfationproducts of butyl oleate, butyl ricinoleate, and the like.

An example of the sulfated olefins includes Teepol (which is a productof Shell Co.).

As salts of carboxymethylation products, salts of carboxymethylationproducts of aliphatic alcohols having 8 to 16 carbon atoms, salts ofcarboxymethylation products of C₈-C₁₆ aliphatic alcohol-EO or PO (1 to10 mol) adducts, and the like can be used.

Examples of the salts of carboxymethylation products of aliphaticalcohols include a sodium salt of carboxymethylated octyl alcohol, asodium salt of carboxymethylated decyl alcohol, a sodium salt ofcarboxymethylated lauryl alcohol, a sodium salt of carboxymethylatedDobanol 23, and a sodium salt of carboxymethylated tridecanol.

Examples of the salts of carboxymethylation products of aliphaticalcohol-EO (1 to 10 mol) adducts include a sodium salt ofcarboxymethylation product of octyl alcohol-EO (3 mol) adduct, a sodiumsalt of carboxymethylation product of lauryl alcohol-EO (4 mol) adduct,a sodium salt of carboxymethylation product of Dobanol 23-EO (3 mol)adduct, and a sodium salt of carboxymethylation product of tridecanol-EO(5 mol) adduct.

As sulfonic acid salts, alkylbenzene sulfonates, alkylnaphthalenesulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates,Igepon T type, other sulfonates of aromatic ring-containing compounds,and the like can be used.

An example of the alkylbenzene sulfonates includes sodiumdodecylbenzensulfonate.

An example of the alkylnaphthalene sulfonates includes sodiumdodecylnaphthalenesulfonate.

An example of the sulfosuccinic acid diester salts includes sodiumdi-2-ethylhexyl sulfosuccinate.

Examples of the sulfonates of aromatic ring-containing compounds includealkylated diphenyl ether mono- or disulfonate and styrenated phenolsulfonate.

As phosphoric acid ester salts, higher alcohol phosphoric acid estersalts, higher alcohol-EO adduct phosphoric acid ester salts, and thelike can be used.

Examples of the higher alcohol phosphoric acid ester salts includelauryl alcohol phosphoric acid monoester disodium salt, and laurylalcohol phosphoric acid diester sodium salt.

An example of the higher alcohol-EO adduct phosphoric acid ester saltsincludes oleyl alcohol-EO (5 mol) adduct phosphoric acid monoesterdisodium salt.

As cationic surfactants (S-2), quaternary ammonium salt-typesurfactants, amine salt-type surfactants, and the like can be used.

The quaternary ammonium salt-type surfactants can be obtained by thereaction between tertiary amines having 3 to 40 carbon atoms andquaternizing agents (e.g., alkylating agents such as methyl chloride,methyl bromide, ethyl chloride, benzyl chloride, and dimethyl sulfate,and EO), and examples of such quaternary ammonium salt-type surfactantsinclude lauryltrimethylammonium chloride, didecyldimethylammoniumchloride, dioctyldimethylammonium bromide, stearyltrimethylammoniumbromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride),cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride, andstearamidoethyldiethylmethylammonium methosulfate.

The amine salt-type surfactants can be obtained by neutralizing primaryto tertiary amines with inorganic acid (e.g., hydrochloric acid, nitricacid, sulfuric acid, hydrogen iodide, phosphoric acid, or perchloricacid) or organic acid (e.g., acetic acid, formic acid, oxalic acid,lactic acid, gluconic acid, adipic acid, alkylphosphoric acid having 2to 24 carbon atoms, malic acid, or citric acid).

Examples of primary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic higher amines having 8 to 40 carbonatoms (e.g., higher amines such as laurylamine, stearylamine,cetylamine, hydrogenated beef tallow amine, and rosin amine), and C₈-C₄₀higher fatty acid (e.g., stearic acid and oleic acid) salts of loweramines having 2 to 6 carbon atoms.

Examples of secondary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic amine (having 4 to 40 carbon atoms)-EOadducts.

Examples of tertiary amine salt-type surfactants include inorganic ororganic acid salts of aliphatic amines having 4 to 40 carbon atoms(e.g., triethylamine, ethyldimethylamine, andN,N,N′,N′-tetramethylethylenediamine), aliphatic amines (having 2 to 40carbon atoms)-EO (2 or more mol) adducts, alicyclic amines having 6 to40 carbon atoms (e.g., N-methylpyrrolidine, N-methylpiperidine,N-methylhexamethyleneimine, N-methylmorpholine, and1,8-diazabicyclo(5,4,0)-7-undecene), nitrogen-containing heterocyclicaromatic amines having 5 to 30 carbon atoms (e.g.,4-dimetylaminopyridine, N-methylimidazole, and 4,4′-dipyridyl), andinorganic or organic acid salts of tertiary amines such astriethanolamine monostearate, stearamidoethyldiethylmethylethanolamine,and the like.

As amphoteric surfactants (S-3), carboxylic acid salt-type amphotericsurfactants, sulfuric acid ester salt-type amphoteric surfactants,sulfonic acid salt-type amphoteric surfactants, phosphoric acid estersalt-type amphoteric surfactants, and the like can be used.

As the carboxylic acid salt-type amphoteric surfactants, aminoacid-based amphoteric surfactants, betaine-type amphoteric surfactants,and imidazoline-type amphoteric surfactants, and the like can be used.The amino acid-type amphoteric surfactant is an amphoteric surfactanthaving an amino group and a carboxyl group in the molecule, and examplesof such amino acid-type amphoteric surfactant include compoundsrepresented by the general formula (2):[R—NH—(CH₂)_(n)—COO]_(m)M  (2)

-   -   wherein R represents a monovalent hydrocarbon group, n is 1 or        2, m is 1 or 2, and M represents a hydrogen ion, an alkali metal        ion, an alkaline-earth metal ion, an ammonium cation, an amine        cation, an alkanolamine cation, or the like.

Examples of the amphoteric surfactants represented by the generalformula (2) include alkyl (having 6 to 40 carbon atoms) aminopropionicacid-type amphoteric surfactants (e.g., sodium stearylaminopropionateand sodium laurylaminopropionate) and alkyl (having 4 to 24 carbonatoms) aminoacetic acid-type amphoteric surfactants (e.g., sodiumlaurylaminoacetate).

The betaine-type amphoteric surfactant is an amphoteric surfactanthaving a quaternary ammonium salt-type cationic moiety and a carboxylicacid-type anionic moiety in the molecule, and examples of such abetaine-type amphoteric surfactant include alkyl (having 6 to 40 carbonatoms) dimethylbetaines (e.g., stearyldimethylaminoacetic acid betaineand lauryldimethylaminoacetic acid betaine), amido betaines having 6 to40 carbon atoms (e.g., coco-fatty acid amidopropyl betaine), and alkyl(having 6 to 40 carbon atoms) dihydroxyalkyl (having 6 to 40 carbonatoms) betaines (e.g., lauryldihydroxyethyl betaine).

The imidazoline-type amphoteric surfactant is an amphoteric surfactanthaving a cationic moiety containing an imidazoline ring and a carboxylicacid-type anionic moiety, and an example of such an imidazoline-typeamphoteric surfactant includes2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

As other amphoteric surfactants, glycine-type amphoteric surfactantssuch as sodium lauroyl glycine, sodium lauryl diaminoethylglycine,lauryldiaminoethylglycine hydrochloride, and dioctyldiaminoethylglycinehydrochloride, sulfobetaine-based amphoteric surfactants such aspentadecylsulfotaurine, sulfonic acid salt-type amphoteric surfactants,and phosphoric acid ester salt-type amphoteric surfactants, and the likecan be used.

As nonionic surfactants (S-4), AO adduct-type nonionic surfactants andpolyhydric alcohol-type nonionic surfactants, and the like can be used.

The AO adduct-type nonionic surfactants can be obtained by directlyadding AO (having 2 to 20 carbon atoms) to higher alcohols having 8 to40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms oralkylamines having 8 to 40 carbon atoms, or by reacting higher fattyacids with polyalkylene glycols obtained by adding AO to glycol, or byadding AO to esterification products obtained by the reaction ofpolyhydric alcohols and higher fatty acids, or by adding AO to higherfatty acid amides.

Examples of AO include EO, PO, and BO.

Among them, EO, and a random or block adduct of EO and PO are preferablyused.

The number of mols of the AO to be added is preferably in the range of10 to 50 mols, and 50 to 100% of the added AO is preferably EO.

Examples of the AO adduct-type nonionic surfactants includeoxyalkylene(C₂-C₂₄) alkyl(C₈-C₄₀) ethers (e.g., octyl alcohol-EO (20mol) adduct, lauryl alcohol-EO (20 mol) adduct, stearyl alcohol-EO (10mol) adduct, oleyl alcohol-EO (5 mol) adduct, and lauryl alcohol-EO (10mol)/PO (20 mol) block adduct), polyoxyalkylene(C₂-C₂₄) higher fattyacid(C₈-C₄₀) esters (e.g., stearic acid-EO (10 mol) adduct and lauricacid-EO (10 mol) adduct), higher fatty acid(C₈-C₄₀) esters ofpolyoxyalkylene(C₂-C₂₄) polyhydric alcohols(C₃-C₄₀), (e.g., polyethyleneglycol (Degree of polymerization of 20) lauric acid diester,polyethylene glycol (Degree of polymerization of 20) oleic acid diester,and polyethylene glycol (Degree of polymerization of 20) stearic aciddiester), polyoxyalkylene(C₂-C₂₄) alykyl(C₈-C₄₀)phenyl ethers (e.g.,nonylphenol-EO (4 mol) adduct, nonylphenol-EO (8 mol)/PO (20 mol) blockadduct, octylphenol-EO (10 mol) adduct, bisphenol A-EO (10 mol) adduct,dinonylphenol-EO (20 mol) adduct, and styrenated phenol-EO (20 mol)adduct), polyoxyalkylene(C₂-C₂₄) alkyl(C₈-C₄₀)amino ethers (e.g.,laurylamine-EO (10 mol) adduct and stearylamine-EO (20 mol) adduct), andpolyoxyalkylene(C₂-C₂₄) alkanolamides (in which amide (acyl moiety) has8 to 24 carbon atoms) (e.g., hydroxyethyl laurylamide-EO (10 mol)adduct, hydroxypropyloleylamide-EO (20 mol) adduct, and dihydroxyethyllaurylamide-EO (10 mol) adduct).

As polyhydric alcohol-type nonionic surfactants, polyhydric alcoholfatty acid esters, polyhydric alcohol fatty acid ester-AO adducts,polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether-AOadducts, and the like can be used. Here, polyhydric alcohols have 3 to24 carbon atoms, fatty acids have 8 to 40 carbon atoms, and AO has 2 to24 carbon atoms.

Examples of the polyhydric alcohol fatty acid esters includepentaerythritol monolaurate, pentaerythritol monooleate, sorbitanmonolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitandilaurate, sorbitan dioleate, and sucrose monostearate.

Examples of the polyhydric alcohol fatty acid ester-AO adducts includeethylene glycol monooleate-EO (10 mol) adduct, ethylene glycolmonostearate-EO (20 mol) adduct, trimethylolpropane monostearate-EO (20mol)/PO (10 mol) random adduct, sorbitan monolaurate-EO (10 mol) adduct,sorbitan monostearate-EO (20 mol) adduct, sorbiatn distearate-EO (20mol) adduct, and sorbitan dilaurate-EO (12 mol)/PO (24 mol) randomadduct.

Examples of the polyhydric alcohol alkyl ethers include pentaerythritolmonobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethylether, sorbitan monostearyl ether, methyl glycoside, and laurylglycoside.

Examples of the polyhydric alcohol alkyl ether-AO adducts includesorbitan monostearyl ether-EO (10 mol) adduct, methyl glycoside-EO (20mol)/PO (10 mol) random adduct, lauryl glycoside-EO (10 mol) adduct, andstearyl glycoside-EO (20 mol)/PO (20 mol) random adduct.

Examples of the synthetic polymeric dispersants (H) include polyvinylalcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene imine,and water-soluble polyurethanes (e.g., reaction products of polyethyleneglycol or polycaprolactone diol with polyisocyanates).

Examples of the solvents (U) used in the methods (1) to (7) to obtainthe aqueous dispersant (I) include aromatic hydrocarbon solvents (e.g.,toluene, xylene, ethylbenzene, and tetralin), aliphatic or alicyclichydrocarbon solvents (e.g., n-hexane, n-heptane, mineral spirit, andcyclohexane), halogen-containing solvents (e.g., methyl chloride, methylbromide, methyl iodide, methylene dichloride, carbon tetrachloride,trichloroethylene, and perchloroethylene), ester or ester ether solvents(e.g., ethyl acetate, butyl acetate, methoxybutyl acetate,methylcellosolve acetate, and ethylcellosolve acetate), ether solvents(e.g., diethyl ether, tetrahydrofuran, dioxane, ethylcellosolve,butylcellosolve, and propylene glycol monomethyl ether), ketone solvents(e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butylketone, and cyclohexanone), alcohol solvents (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexylalcohol, and benzyl alcohol), amide solvents (e.g., dimethylformamideand dimethylacetamide), sulfoxide solvents (e.g., dimethylsulfoxide),heterocyclic compound solvents (e.g., N-methylpyrrolidone), and mixturesof two or more of them.

Among these solvents, from the viewpoint of easiness of removingsolvents, aromatic hydrocarbon solvents, halogen-containing solvents,ester or ester ether solvents, ketone solvents, and alcohol solvents arepreferably used, more preferably ester or ester ether solvents, ketonesolvents and alcohol solvents.

The plasticizer (L) to be used is not limited to any specific one, andthe above-mentioned plasticizers (L1) to (L5) and mixtures of two ormore of them can be used. A preferred range of the amount of theplasticizer to be used is the same as described above.

The amount of an aqueous medium to be used with respect to 100 parts ofthe resin (a) is preferably in the range of 50 to 2,000 parts, morepreferably in the range of 100 to 1,000 parts, even more preferably inthe range of 100 to 500 parts. If the amount of an aqueous medium to beused is less than above lower limit, dispersibility of the resin (a)tends to be lowered. On the other hand, if the amount of an aqueousmedium to be used exceeds the above upper limit, economic problems tendto arise.

It should be noted that the aqueous medium is not limited to anyspecific one as long as it is a liquid containing water as an essentialcomponent. Examples of such an aqueous medium include water, aqueoussolutions of solvents, aqueous solutions of the surfactants (S), aqueoussolutions of the synthetic polymeric dispersants (H), and mixtures oftwo or more of them.

Examples of the solvents include, among the solvents (U) mentionedabove, ester or ester ether solvents, ether solvents, ketone solvents,alcohol solvents, amide solvents, sulfoxide solvents, heterocycliccompound solvents, and mixtures of two or more of them.

In a case where the aqueous medium contains such a solvent, the amountof the solvent contained in the aqueous medium is preferably in therange of 1 to 80%, more preferably in the range of 2 to 70%, even morepreferably in the range of 5 to 30% with respect to the weight of theaqueous medium.

In a case where the surfactant (S) is used, the amount of the surfactant(S) contained in the aqueous medium is preferably in the range of 0.001to 0.3%, more preferably in the range of 0.005 to 0.2%, even morepreferably in the range of 0.01 to 0.15% with respect to the weight ofthe aqueous medium.

In a case where the synthetic polymeric dispersant (H) is used, theamount of the synthetic polymeric dispersant (H) contained in theaqueous medium is preferably in the range of 0.0001 to 0.2%, morepreferably in the range of 0.0002 to 0.15%, even more preferably in therange of 0.0005 to 0.1% with respect to the weight of the aqueousmedium.

When the resin (a) and/or the precursor (a0) is dispersed in the aqueousmedium, the resin (a) and the precursor (a0) are preferably in the formof liquid or solution. In a case where the resin (a) and the precursor(a0) are solid at room temperatures, the resin (a) and the precursor(a0) may be dispersed at a temperature of the melting point thereof orhigher so that they can be dispersed in liquid form, or a solutionobtained by dissolving the resin (a) and the precursor (a0) in theabove-mentioned solvent (U) may be used.

In a case where the solvent (U) is used, a preferred solvent depends onthe kind of resin (a) and precursor (a0) to be used, but the differencein SP value between the resin (a) and the precursor (a0) is preferably 3or less.

The viscosities of the resin (a), the precursor (a0), and solventsolutions thereof are preferably in the range of 10 to 50,000 mPa·s,more preferably in the range of 100 to 30,000 mPa·s, even morepreferably in the range of 200 to 20,000 mPa·s, from the viewpoint ofparticle size uniformity.

In this regard, it is to be noted that all viscosities in thisspecification were measured using a rotor-type viscometer such as aBL-type viscometer, a BM-type viscometer, or a BH-type viscometer (whichare manufactured by Tokyo Instruments Co., Ltd.) at a temperature of 25°C.

A temperature at the time of dispersion is preferably in the range of 0to 150° C., more preferably in the range of 5 to 98° C., even morepreferably in the range of 10 to 60° C. In this regard, it is to benoted that a temperature exceeding 100° C. refers to a temperature underpressure.

In a case where the solvent is used, the concentration of the resin isdetermined so that the viscosity of the solution thereof becomes a valuewithin the above-mentioned preferred range, and is preferably in therange of 5 to 95%, more preferably in the range of 10 to 90%, even morepreferably in the range of 20 to 80%.

The method for preparing resin particles according to the presentinvention comprises a step of applying a shear force to an aqueousdispersion (II) with increased viscosity formed by adding a thickener(V) to the dispersant (I) containing the resin particles (A) obtained insuch a manner as described above, and a subsequent step of decreasingthe viscosity of the aqueous dispersant.

As such a thickener (V), water-soluble naturally-occurring polymers(e.g., polysaccharide-based naturally-occurring polymers andanimal-based naturally-occurring polymers), water-soluble semisyntheticpolymers (e.g., cellulose-based semisynthetic polymers, starch-basedsemisynthetic polymers, and alginic acid-based semisynthetic polymers),water-soluble synthetic polymers (e.g., acrylic acid-based (co)polymersalts, vinyl ether-based (co)polymers, and acrylamide-based(co)polymers), and the like can be used.

Examples of the water-soluble naturally-occurring polymers include, butnot limited to, polysaccharide-based naturally-occurring polymers (e.g.,pullulan, guar gum, locast bean gum, gum Arabic, and starch), andanimal-based naturally-occurring polymers (e.g., gelatin and casein).

Examples of the water-soluble semisynthetic polymers include, but notlimited to, cellulose-based semisynthetic polymers (e.g., methylcellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethylcellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, andsodium carboxymethyl cellulose), starch-based semisynthetic polymers(e.g., soluble starch, carboxymethyl starch, methyl starch, andcationized starch), and alginic acid-based semisynthetic polymers (e.g.,alginic acid salts, chitin, and chitosan).

The water-soluble synthetic polymeric thickeners can be obtained by awell-known polymerization method using a well-known catalyst.

Examples of the acrylic acid-based (co)polymers include a polymer ofacrylic acid and copolymers of acrylic acid and other monomers. As suchother monomers, the above-mentioned vinyl monomers (1) to (10) can beused. The amount of acrylic acid contained in the copolymer is generally60% or more.

Examples of the acrylic acid-based (co)polymer salts include alkalimetal salts (e.g., sodium salts and potassium salts), ammonium salts,amine salts, and quaternary ammonium salts. Amine salts to be used arenot limited to any specific ones as long as they are amine compounds,and examples of such amine salts include primary amine salts (e.g.,ethylamine salts, butylamine salts, and octylamine salts), secondaryamine salts (e.g., diethylamine salts and dibutylamine salts), andtertiary amine salts (e.g., triethylamine salts and tributylaminesalts). Examples of quaternary amine salts include tetraethylammoniumsalts, lauryltriethylammonium salts, tetrabutylammonium salts, andlauryltributylammonium salts.

Examples of the vinyl ether-based (co)polymers include (co) polymers ofvinyl alkyl ethers having 3 to 6 carbon atoms (e.g., vinyl methyl ether,vinyl ethyl ether, vinyl propyl ether and vinyl butyl ether), vinylalcohol-EO adducts, urethane-modified vinyl ether obtained by joiningvinyl alcohol to polyethylene glycol by the use of polyisocyanate (15),and mixtures of two or more of them.

Examples of the acrylamide-based (co)polymers include (co)polymers ofacrylamide, N-alkyl(C₁-C₄)acrylamides (e.g., N-methylacrylamide,N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, andN-butylacrylamide), N,N-dialkyl(C₁-C₄)acrylamides (e.g.,N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide,N,N-diisopropylacrylamide, and N,N-butylacrylamide), and mixtures of twoor more of them, and salts of copolymers of acrylamide,N-alkyl(C₁-C₄)acrylamide, N,N-dialkyl(C₁-C₄ alkyl) acrylamide andmixtures of two or more of them with acrylic acid.

In a case where acrylic acid is used in forming a copolymer, the amountof acrylic acid contained in the copolymer is generally less than 40%.

As salts of copolymers formed using acrylic acid, the same salts ofacrylic acid-based (co)polymers as mentioned above can be mentioned.

The Mw of the water-soluble synthetic polymeric thickener is preferablyin the range of 1,000 to 10,000,000, more preferably in the range of2,000 to 1,000,000.

Among these thickeners (V) mentioned above, cellulose-basedsemisynthetic polymers, acrylic acid-based (co)polymer salts, and vinylether-based (co)copolymers are preferably used, more preferably sodiumsalts of acrylic acid-based polymers, hydroxyethyl cellulose, andcarboxymethyl cellulose, even more preferably carboxymethyl cellulose.

The amount of the thickener (V) to be added depends on the kind thereofto be used, but is preferably in the range of 0.0001 to 10%, morepreferably in the range of 0.001 to 5%, even more preferably in therange of 0.01 to 2% with respect to the weight of the aqueous dispersion(I).

The viscosity of the aqueous dispersion (II) with increased viscosity(at 25° C.) is preferably in the range of 300 to 100,000 mPa·s. Thelower limit is more preferably 1,000 mPa·s, even more preferably 2,000mPa·s. The upper limit is more preferably 60,000 mPa·s, even morepreferably 20,000 mPa·s By setting the viscosity of the aqueousdispersion (II) to a value within the above range, it is possible toreduce the time for deforming resin particles by the application of ashear force. In addition, it is also possible to obtain a dispersion inwhich the deformed resin particles are hard to return to spherical resinparticles, that is, it is possible to obtain a dispersion in whichdeformed resin particles are stable in their shape.

A method for deforming the resin particles (A) by the application of ashear force to the aqueous dispersion (II) is not particularly limited,and a well-known method can be used.

An apparatus to be used in applying a shear force is not limited to anyspecific one as long as it is commercially available as an agitator or adispersing machine. Examples of trade names of such commerciallyavailable dispersing machines include batch-type dispersing machinessuch as Homogenizer (manufactured by IKA), Polytron (manufactured byKINEMATICA), and TK Auto Homomixer (manufactured by Tokushu Kika KogyoCo., Ltd.), continuous-type dispersing machines such as Ebara Milder(manufactured by Ebara Corporation), TK Filmics and TK PipelineHomomixer (which are manufactured by Tokushu Kika Kogyo Co., Ltd.),Colloid Mill (manufactured by Shinko Pantec Co., Ltd.), Slusher andTrigonal Wet Mill (which are manufactured by Mitsui Miike Kakoki K.K.),Cavitron (manufactured by EUROTEC Ltd.), and Fine Flow Mill(manufactured by Pacific Machinery & Engineering Co., Ltd.),high-pressure dispersing machines such as Microfluidizer (manufacturedby Mizuho Industrial Co., Ltd.), Nanomizer (manufactured by NanomizerInc.), and APV Gaulin (manufactured by Gaulin Inc.), membrane dispersingmachines such as Membrane Dispersing Machine (manufactured by REICA Co.,Ltd.), vibration-type dispersing machines such as Vibromixer(manufactured by REICA CO., Ltd.), and ultrasonic dispersing machinessuch as Ultrasonic Homogenizer (manufactured by BRANSON).

Among these dispersing machines, from the viewpoint of application of auniform shear force, APV Gaulin, Homogenizer, TK Auto Homomixer, EbaraMilder, TK Filmics, and TK Pipeline Homomixer are preferably used, morepreferably TK Auto Homomixer, Ebara Milder, TK Filmics, and TK PipelineHomomixer, even more preferably TK Auto Homomixer, TK Filmics, and TKPipeline Homomixer.

A temperature at the time of applying a shear force is not limited toany specific value, but is preferably in the range of 0 to 60° C., morepreferably in the range of 5 to 50° C., even more preferably in therange of 10 to 40° C., from the viewpoint of easiness of deformation ofresin particles and prevention of coagulation of resin particles.

The length of time for the application of a shearing force depends onthe kind of apparatus to be used, and is not particularly limited.However, from the viewpoint of easiness of deformation of resinparticles and productivity, the length of time for the application of ashear force is preferably in the range of 0.01 second to 6 hours, morepreferably in the range of 0.01 second to 1 hour, even more preferablyin the range of 0.01 second to 50 minutes, most preferably in the rangeof 0.1 second to 20 minutes.

A shear force to be applied varies depending on the viscosity of theaqueous dispersion (II), the length of time for the application of ashear force, and the temperature at the time of application of a shearforce, and can be appropriately determined. However, from the viewpointof easiness of deformation of resin particles and easiness of particlediameter control, a shear force is preferably applied at 10 to 50,000rpm by, for example, the above-mentioned apparatus for applying ashearing force. The lower limit thereof is more preferably at 100 rpm,even more preferably at 500 rpm. The upper limit thereof is morepreferably at 20,000 rpm, even more preferably at 10,000 rpm.

As a method for decreasing the viscosity of the aqueous dispersion afterthe application of a shear force, the following methods (1) to (3) and acombination of two or more of them can be employed:

-   -   (1) a method in which the viscosity of the aqueous dispersion is        reduced by controlling the pH thereof;    -   (2) a method in which a viscosity reducing agent (E) is added to        reduce the viscosity of the aqueous dispersion; and    -   (3) a method in which the viscosity of the aqueous dispersion is        reduced by controlling the temperature thereof.

In the method (1), a preferred pH of the aqueous dispersion can beappropriately selected according to the kind of thickener used and atarget viscosity, but the pH of the aqueous dispersion is preferably inthe range of 1 to 9, more preferably in the range of 1 to 6, even morepreferably in the range of 2 to 4. It is preferred that the pH isadjusted by adding inorganic acid such as hydrohalic acid (e.g.,hydrofluoric acid, hydrochloric acid, or hydrobromic acid), sulfuricacid, nitric acid, phosphoric acid, or perchloric acid, or organic acidsuch as acetic acid, oxalic acid, or carbonic acid, in the form ofaqueous solution (e.g., 2 to 40%) as necessary. Among them, inorganicacids (aqueous solutions) are more preferably used, even more preferablyan aqueous hydrochloric acid solution and an aqueous phosphoric acidsolution. The method (1) is suitably used in a case where thewater-soluble synthetic polymer is used as the thickener (V).

The viscosity reducing agent (E) to be used in the method (2) depends onthe kind of thickener used and a target viscosity, and examples of theviscosity reducing agent include enzymes, inorganic acid salts, andorganic acid salts.

An enzyme is suitably used in a case where the water-solublenaturally-occurring polymer and/or the water-soluble semisyntheticpolymer is used as the thickener (V). Examples of such an enzyme includeα-glycanase (e.g., amylase, dextranase, or pullulanase) and β-glycanase(e.g., cellulase, β-1,3-glucanase, or chitinase). These enzymes can beused in combination of two or more of them.

Examples of inorganic acid salts and organic acid salts include, but notlimited to, alkali metals salts (e.g., sodium salts and potassium salts)and alkaline-earth metal salts (e.g., magnesium salts and calcium salts)of the inorganic acids and the organic acids mentioned above.

From the viewpoint of productivity (e.g., time for decreasing viscosity)and manufacturing costs, the amount of the enzyme to be added ispreferably in the range of 0.000001 to 1%, more preferably in the rangeof 0.000005 to 0.1%, even more preferably in the range of 0.00001 to0.01% with respect to the weight of the aqueous dispersion (II).

The amount of the inorganic or organic acid salt to be added is notlimited to any specific value, but, from the viewpoint of a viscosityreduction effect and manufacturing costs, is preferably in the range of0.0001 to 15%, more preferably in the range of 0.001 to 10%, even morepreferably in the range of 0.01 to 5% with respect to the weight of theaqueous dispersion.

The method (3) is particularly effective in a case where the viscosityincreasing effect of the thickener used has a dependence on temperature.For example, in a case where the acrylamide-based (co)polymer is used asthe thickener, the viscosity of the aqueous dispersion can be reduced bydecreasing the temperature thereof.

Among these methods (1) to (3), the method (1) and (2) are preferablyemployed. More preferably, the method (2) using an enzyme as a viscositydecreasing agent is employed because the viscosity of the aqueousdispersion can be quickly decreased.

A decreased viscosity (at 25°) of the aqueous dispersion is preferably200 mPa·s or less. The upper limit is more preferably 100 mPa·s, evenmore preferably 60 mPa·s, the lower limit is more preferably 10 mPa·s.By setting the decreased viscosity of the aqueous dispersion to a valuewithin the above range, it becomes easy to handle the aqueous dispersionuntil resin particles (B) are obtained. In addition, it becomes easy towash the aqueous dispersion in a washing process (which will bedescribed later) carried out as necessary.

A temperature at the time of carrying out the viscosity decreasing stepis not limited to any specific value, but is preferably in the range of5 to 40° C., more preferably in the range of 10 to 35° C., even morepreferably in the range of 20 to 30° C., from the viewpoint ofproductivity and a viscosity reduction effect.

The length of time of the viscosity decreasing step is not limited toany specific value, but is preferably 3 hours or less, more preferably1.5 hours or less, even more preferably in the range of 0.5 to 20minutes, from the viewpoint of productivity.

In a case where a solvent has been used at the time of producing theaqueous dispersion (I), the solvent is removed by, for example, heating,decompression, washing with water, or a combination of two or more ofthem.

In a case where the thickener (V) and the surfactant (S) used adverselyaffect the physical properties of the resin particles (B) in use, theseadditives are preferably removed.

An example of a method for removing such additives includes a method, inwhich the aqueous dispersion is subjected to solid-liquid separation bya centrifuge, a sparkler filter and/or a filter press to obtain resinparticles, water is added to the resin particles to again carry outsolid-liquid separation with such a means mentioned above, and thelatter process is repeatedly carried out.

The aqueous dispersion of the resin particles (B) obtained in such amanner as described above is subjected to solid-liquid separation (asnecessary, solid-liquid separation is repeatedly carried out by addingwater or the like), and then the obtained resin particles are dried toremove the aqueous medium, thereby enabling the resin particles (B) ofthe present invention to be obtained.

As a method for removing the aqueous medium, the following methods (1)to (3) and a combination of two or more of them can be employed:

-   -   (1) a method in which the aqueous dispersion is dried under        reduced pressure or normal atmospheric pressure;    -   (2) a method in which solid-liquid separation is carried out        with a centrifuge, a sparkler filter and/or a filter press, and        the resulting solid is dried; and    -   (3) a method in which the aqueous dispersion is freeze-dried        (the so-called lyophilization).

In the methods (1) and (2), drying can be carried out by well-knownmachines such as a fluidized-bed type dryer, a vacuum dryer, and anair-circulation dryer.

As necessary, the obtained resin particles may be classified with an airclassifier or a screen to attain a predetermined particle sizedistribution.

The ellipticity of the resin particles (B) obtained by the preparingmethod according to the present invention is expressed in terms of ashape factor (hereinafter, simply referred to as “SF-1”). The SF-1 ofthe resin particles (B) is preferably in the range of 110 to 800. Theupper limit is more preferably 500, still more preferably 400, even morepreferably 300, still even more preferably 250, most preferably 200. Thelower limit is more preferably 120, still more preferably 130, mostpreferably 140. By setting the SF-1 to a value within the above range,it is possible to obtain the following effects according to the purposesof use of the resin particles.

Specifically, in a case where the resin particles are used as anadditive for paint or an additive for coating materials, such resinparticles show significant thixotropy when dispersed in a solvent or anaqueous medium, and therefore the resin particles are particularlyuseful as a fluidity improving agent for paint and coating materials.Further, since the resin particles are aligned uniformly in thedirection of a longer diameter thereof in the formation of a coating,the effect of preventing blister from occurring in forming a coating andthe effect of improving luster or a gloss of a coating can be obtained.

In this regard, it is to be noted that, in a case where the resinparticles are to be used as an additive for paint or an additive forcoating materials, the SF-1 of the resin particles is preferably in therange of 110 to 800. The upper limit is more preferably 500, even morepreferably 300, the lower limit is most preferably 120, even morepreferably 130, most preferably 140.

Further, in a case where the resin particles are used as an additive forcosmetics (e.g., lipstick and foundation), the resin particlesfacilitate smooth feeling when such cosmetics are applied to the skin.In a case where the resin particles are used as a resin for slushmolding or a hot-melt adhesive, powder fluidity and powder releaseproperties at the time of application are improved.

In this regard, it is to be noted that, in a case where the resinparticles are to be used as an additive for cosmetics (e.g., lipstickand foundation), a resin for slush molding, or a hot-melt adhesive, theSF-1 of the resin particles is preferably in the range of 110 to 500.The upper limit is more preferably 300, even more preferably 200, thelower limit is more preferably 120, even more preferably 130, mostpreferably 140.

Furthermore, in a case where the resin particles are used as a toner forelectrophotography, electrostatic recording or electrostatic printing,cleaning of the toner with a cleaning blade is facilitated.

In this regard, it is to be noted that, in a case where the resinparticles are to be used as a toner for electrophotography,electrostatic recording, or electrostatic printing, the SF-1 of theresin particles is preferably in the range of 110 to 400. The upperlimit is more preferably 300, even more preferably 250, the lower limitis more preferably 120, even more preferably 130, most preferably 140.

In the present invention, the shape factor (SF-1) is determined byrandom sampling 100 images of the resin particles obtained by scaling up500 times by the use of an electronic microscope (e.g., “FE-SEM (S-800)”which is manufactured by Hitachi, Ltd; the same applies to the followingdescription), inputting the image data into an image analyzer (e.g.,“nexus NEW CUBE ver.2.5” manufactured by NEXUS Co., Ltd. and “Luzex III”manufactured by NIRECO Corporation; the same applies to the followingdescription) via an interface to analyze the image data, and carryingout calculation using the formula (1):(SF-1)=100πL ²/4S  (1)

-   -   wherein L represents the absolute longest length of the resin        particle and S represents the projected area of the resin        particle.

The volume average particle diameter (hereinafter, simply referred to as“DV”) of the resin particles (B) obtained by the preparing methodaccording to the present invention is preferably in the range of 0.1 to300 μm, more preferably in the range of 0.5 to 250 μm, even morepreferably in the range of 1 to 200 μm. By setting the DV to a valuewithin the above range, the SF-1 of the resin particles (B) can liewithin the preferred range described above.

In this regard, it is to be noted that the volume average particlediameter can be measured by a laser type particle size analyzer (e.g.,“LA-920” which is a product of HORIBA, Ltd. or “Multisizer III” which isa product of Beckman Coulter).

In a case where it is necessary to improve the powder fluidity of theresin particles (B), the BET specific surface area of the resinparticles (B) is preferably in the range of 0.5 to 8 m²/g, morepreferably in the range of 0.7 to 5 m²/g.

In this regard, it is to be noted that the BET specific surface area canbe measured with a specific surface area meter (e.g., “QUANTASORB” whichis a product of Yuasa Ionics Inc.) (Measuring gas: He/Kr=99.9/0.1 vol %,Calibration gas: nitrogen).

Similarly, from the viewpoint of powder fluidity, the average of surfaceroughness (Ra) of the resin particles (B) is preferably in the range of0.01 to 0.8 μm, more preferably in the range of 0.1 to 0.7 μm.

In this regard, it is to be noted that the (Ra) is the arithmetical meanvalue of the absolute values of the deviation between the roughnesscurve and the centerline thereof, and can be measured by a scanningprobe microscope system (manufactured by, for example, ToyoCorporation).

The resin particles (B) according to the present invention can besuitably used as additives for paint, additives for coating materials,powder coatings, additives for cosmetics, resins for slush molding,spacers for use in manufacturing electronic components or devices suchas liquid crystal displays, standard particles for electronic measuringinstruments, toners for electrophotography, electrostatic recording, andelectrostatic printing, hot-melt adhesives, and other molding materials.

EXAMPLES

The present invention will be further described with reference to thefollowing examples, but the present invention is not limited to theseexamples.

Production Example 1

In a reaction vessel equipped with a stirring rod and a thermometer, 787parts of polycaprolactonediol (Mn 2,000) and 800 parts of polyether diol(Mn 4,000, EO content 50 wt %, PO content 50 wt %) were placed, and werethen subjected to dehydration under reduced pressure at 120° C. Thewater content after dehydration was 0.05%. After cooling to 60° C., 55.5parts of HDI, 65.5 parts of hydrogenated MDI and 0.6 part of dibutyltindilaurate were added, and then a reaction was carried out for 5 hours at80° C., to thereby obtain a synthetic polymeric dispersant (1).

Further, 1 part of the synthetic polymeric dispersant (1) was mixed with200 parts of water with stirring to obtain a milk white dispersant (1).

Production Example 2

In a reaction vessel equipped with a stirring rod and a thermometer,2,000 parts of polycaprolactonediol having a hydroxyl value of 56(“PLACCEL L220 AL” manufactured by Daicel Chemical Industries, Ltd.) wasplaced, and was then subjected to dehydration for 1 hour under heatingto 110° C. at a reduced pressure of 3 mmHg. Then, 457 parts of IPDI wasadded, and a reaction was carried out for 10 hours at 110° C., tothereby obtain an isocyanate-terminated urethane prepolymer (1). The NCOcontent of the urethane prepolymer (1) was 3.6%.

Production Example 3

In a reaction vessel equipped with a stirring rod and a thermometer, 50parts of ethylenediamine and 50 parts of methyl isobutyl ketone wereplaced, and then a reaction was carried out for 5 hours at 50° C., tothereby obtain a ketimine compound [curing agent (1)].

Production Example 4

In a reaction vessel equipped with a stirring rod and a thermometer, 100parts of ethyl acetate and 50 parts of adipic acid, and 55 parts ofethylene glycol were placed. Then, 0.05 part of tributyl titanate wasfurther added, and a reaction was carried out for 7 hours at 170° C., tothereby obtain a polyester solution (1).

Production Example 5

In a reaction vessel equipped with a stirring rod and a thermometer, 683parts of water, 11 parts of methacrylic acid-EO adduct sulfuric acidester sodium salt (“ELEMINOL RS-30” manufactured by Sanyo ChemicalIndustries, Ltd.), 83 parts of styrene, 83 parts of methacrylic acid,110 parts of butylacrylate, 1 part of ammonium persulfate were placed,and were then stirred for 15 minutes at 400 rpm, to thereby obtain awhite emulsion.

The emulsion was heated to 75° C. and was reacted for 5 hours. Further,30 parts of a 1% aqueous ammonium persulfate solution was added, andthen the resulting mixture was matured for 5 hours at 75° C., to therebyobtain an aqueous dispersion of vinyl resin (copolymer ofstyrene-methacrylic acid-butyl acrylate-methacrylic acid-EO adductsulfuric acid ester sodium salt) [microparticle dispersion (1)].

The volume average particle diameter of the microparticle dispersion (1)as measured with LA-920 was 0.10 μm. A part of the microparticledispersion (1) was dried to isolate a resin fraction. The Tg of theresin fraction was 57° C.

Production Example 6

990 parts of water, 83 parts of the microparticle dispersion (1), 52parts of a 48.5% aqueous sodium dodecyl diphenyl ether disulfonatesolution (“ELEMINOL MON-7” manufactured by Sanyo Chemical Industries,Ltd.), and 90 parts of ethyl acetate were mixed with stirring to obtaina milk white liquid. The obtained liquid was defined as a water phase(1).

Production Example 7

In a reaction vessel equipped with a condenser, a stirrer, and anitrogen inlet pipe, 220 parts of bisphenol A-EO (2 mol) adduct, 561parts of bisphenol A-PO (3 mol) adduct, 218 parts of terephthalic acid,48 parts of adipic acid and 2 parts of dibutyltin oxide were placed, andthen a reaction was carried out for 8 hours at normal atmosphericpressure at 230° C., and was further carried out for 5 hours at areduced pressure of 10 to 15 mmHg. Then, 45 parts of trimelliticanhydride was added to the reaction vessel, and a reaction was carriedout for 2 hours at a normal atmospheric pressure at 180° C., to obtainpolyester (1). The obtained polyester (1) had an Mn of 2,500, an Mw of6,700, a Tg of 43° C., and an acid value of 25.

Production Example 8

In a reaction vessel equipped with a condenser, a stirrer, and anitrogen inlet pipe, 682 parts of bisphenol A-EO (2 mol) adduct, 81parts of bisphenol A-PO (2 mol) adduct, 283 parts of terephthalic acid,22 parts of trimellitic anhydride, and 2 parts of dibutyltin oxide wereplaced, and then a reaction was carried out for 8 hours at a normalatmospheric pressure at 230° C., and was further carried out for 5 hoursat a reduced pressure of 10 to 15 mmHg, to obtain an intermediatepolyester (1). The intermediate polyester (1) had an Mn of 2,100, an Mwof 9,500, a Tg of 55° C., an acid value of 0.5, and a hydroxyl value of49.

Next, in a reaction vessel equipped with a condenser, a stirrer, and anitrogen inlet pipe, 411 parts of the intermediate polyester (1), 89parts of isophorone diisocyanate, and 500 parts of ethyl acetate wereplaced, and then a reaction was carried out for 5 hours at 100° C., tothereby obtain an isocyanate-terminated urethane prepolymer (2). Theamount of the free isocyanate contained in the urethane prepolymer (2)was 1.53 wt %.

Production Example 9

In a reaction vessel equipped with a stirring rod and a thermometer, 170parts of isophoronediamine and 75 parts of methyl ethyl ketone wereplaced, and then a reaction was carried out for 5 hours at 50° C., tothereby obtain a ketimine compound 2 [curing agent (2)].

Example 1

In a beaker, 140 parts of the urethane prepolymer (1) obtained inProduction Example 2, 5 parts of the curing agent (1) obtained inProduction Example 3, 50 parts of ethyl acetate were mixed, and then 465parts of water and 3 parts of dodecylnaphthalenesulfonic acid sodiumsalt were added. Thereafter, they were mixed with a TK Homomixer(manufactured by Tokushu Kika Kogyo Co., Ltd.) for 1 minute at 12,000rpm at 25° C., to thereby obtain an aqueous dispersion (X1-1).

To 100 parts of the aqueous dispersion (X1-1), 1.5 parts of sodiumpolyacrylate copolymer (“Carbopol” manufactured by BF Goodrich Co.), andthe resulting mixture was stirred with a TK Homomixer for 8 minutes at2,500 rpm at 25° C., to thereby obtain a dispersion (X1-2). Theviscosity of the (X1-2) was 5,300 mPa·s. Further, 0.1 part of a 10%aqueous hydrochloric acid solution was added, and then the resultingmixture was stirred for 5 minutes at 25° C., to thereby obtain an(X1-3). The pH and the viscosity of the (X1-3) were 3.5 and 60 mPa·s,respectively.

100 parts of (X1-3) was centrifuged. After addition of 60 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (Y-1) were obtained. The physical properties of theresin particles (Y-1) are shown in Table 1.

Example 2

To 100 parts of the aqueous dispersion (X1-1) obtained in Example 1, 4parts of polyvinyl ether copolymer (“SN thickener 621N” manufactured bySan Nopco Limited) was added, and then they were stirred with a TKHomomixer at 2, 500 rpm for 8 minutes at 25° C., to thereby obtain adispersion (X2-2). The viscosity of the (X2-2) was 4,000 mPa·s. Further,0.15 part of a 30% aqueous phosphoric acid solution was added, and theresulting mixture was stirred for 5 minutes at 25° C. to obtain an(X2-3). The pH and viscosity of the (X2-3) were 4.0 and 55 mPa·s,respectively.

100 parts of the (X2-3) was centrifuged. After addition of 60 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (Y-2) were obtained. The physical properties of the(Y-2) are shown in Table 1.

Example 3

In a reaction vessel equipped with a stirring rod and a thermometer, 48parts of styrenated phenol-EO adduct (“ELEMINOL HB-12” manufactured bySanyo Chemical Industries Ltd.) and 241 parts of bisphenol A diglycidylether (“Epikote 828” manufactures by Yuka Shell) were placed, and thenthey were homogeneously dissolved.

Next, water was dropped into the reaction vessel under stirring. At thetime when the amount of water dropped had reached to 31 parts, thecontent of the reaction vessel was emulsified so that the color thereofbecame milk white. 236 parts of water was further added, to obtain adispersion.

After the obtained dispersion was heated to 73° C., a mixed solution of20 parts of ethylenediamine and 446 parts of water was dropped into thedispersion over 2 hours, with the internal temperature of the reactionvessel being maintained at 73° C.

After the completion of dropping, a reaction was carried out for 4 hoursat 73° C., and then a reaction product was matured for 4 hours at 90°C., to thereby obtain an aqueous dispersion (X3-1).

To 100 parts of the (X3-1), 3 parts of carboxymethyl cellulose(“CELLOGEN HH” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) wasadded, and then they were stirred with a Homogenizer (manufactured byIKA) at 1,000 rpm for 10 minutes at 25° C. to obtain a dispersion(X3-2). The viscosity of the dispersion (X3-2) was 3,300 mPa·s. Further,0.02 part of amylase was added, and the resulting mixture was stirredfor 3 minutes at 25° C. to obtain a dispersion (X3-3). The viscosity ofthe dispersion (X3-3) was 50 mPa·s.

103 parts of the (X3-3) was centrifuged. After addition of 50 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (Y-3) were obtained. The physical properties of the(Y-3) are shown in Table 1.

Example 4

In a beaker, 140 parts of the urethane prepolymer (1) and 5 parts of thecuring agent (1) were mixed, and then 265 parts of the dispersion (1)obtained in Production Example 1 was added thereto. Then, they weremixed with an Ultra-disperzer (manufactured by Yamato Scientific Co.,Ltd.) at 9,000 rpm for 1 minute at 25° C., to obtain an aqueousdispersion (X4-1).

To 100 parts of the (X4-1), 1 part of carboxymethyl cellulose (“CELLOGENF-3H” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and then theywere stirred for 10 minutes at 25° C., to obtain a dispersion (X4-2).The viscosity of the (X4-2) was 5,600 mPa·s. The (X4-2) was stirred witha TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 3,000rpm for 10 minutes at 25° C.

Further, 0.01 part of cellulase (“Cellulase AP3” manufactured by AmanoEnzyme Inc.) was added, and the resulting mixture was stirred for 5minutes at 25° C., to obtain a dispersion (X4-3). The viscosity of the(X4-3) was 20 mPa·s.

100 parts of the (X4-3) was centrifuged. After addition of 40 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (Y-4) were obtained. The physical properties of the(Y-4) are shown in Table 1.

Example 5

To 100 parts of the aqueous dispersion (X1-1) obtained in Example 1, 2parts of carboxymethyl cellulose (“CELLOGEN HH” manufactured by DaiichiKogyo Seiyaku Co., Ltd.) was added, and then they were stirred with a TKHomomixer at 2,500 rpm for 8 minutes at 25° C., to thereby obtain adispersion (X5-2). The viscosity of the (X5-2) was 4,900 mPa·s. Further,0.05 part of cellulase (“Celluclast” manufactured by Novozymes JapanLtd.) was added, and the resulting mixture was stirred for 5 minutes at25° C., to obtain (X5-3). The viscosity of the (X5-3) was 40 mPa·s.

100 parts of the (X5-3) was centrifuged. After addition of 60 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (Y-5) were obtained. The physical properties of the(Y-5) are shown in Table 1.

Example 6

In a beaker, 200 parts of the polyester solution (1) obtained inProduction Example 4 was placed, and then 400 parts of water and 5 partsof dodecylnaphthalenesulfonic acid sodium salt were added thereto. Then,they were mixed with a TK Homomixer (manufactured by Tokushu Kika KogyoCo., Ltd.) at 7,000 rpm for 1 minute at 25° C., to thereby obtain anaqueous dispersion (X6-1).

To 100 parts of the (X6-1), 3 parts of carboxymethyl cellulose(“CELLOGEN HH” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) wasadded, and then they were stirred with a TK Homomixer at 5,000 rpm for 1minute at 25° C., to obtain a dispersion (X6-2). The viscosity of the(X6-2) was 6,200 mPa·s. Further, 0.01 part of cellulase (“Cellulase AP3”manufactured by Amamo Enzyme Inc.) was added, and the resulting mixturewas stirred for 3 minutes at 25° C., to obtain a dispersion (X6-3). Theviscosity of the (X6-3) was 20 mPa·s. The (X6-3) was charged into avessel equipped with a stirrer and a thermometer, and removal of solventwas carried out for 2 hours at 30° C., to obtain a dispersion (X6-4).

100 parts of the (X6-4) was centrifuged. After addition of 50 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 12 hours at 36° C.,resin particles (Y-6) were obtained. The physical properties of the(Y-6) are shown in Table 2.

Example 7

682 parts of the polyester (1), 120 parts of the urethane prepolymer(2), and 5.5 parts of the curing agent (2) obtained in ProductionExamples 7 to 9, respectively were placed in a vessel, and they werestirred with a TK Homomixer (manufactured by Tokushu Kika Kogyo Co.,Ltd.) at 5,000 rpm for 1 minute. 1,200 parts of the water phase (1)obtained in Production Example 6 was added to the vessel, and theresulting mixture was stirred with a TK Homomixer at 11,000 rpm for 1minute, to obtain an aqueous dispersion (X7-1).

To 100 parts of the aqueous dispersion (X7-1), 150 parts of water wasadded, and then 6 parts of carboxymethyl cellulose (“CELLOGEN HH”manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added. Then, theywere stirred with a TK Homomixer at 6,000 rpm for 2 minutes at 25° C.,to obtain a dispersion (X7-2). The viscosity of the (X7-2) was 5,800mPa·s. Further, 0.015 part of cellulase (“Cellulase AP3” manufactured byAmano Enzyme Inc.) was added, and the resulting mixture was stirred for3 minutes at 25° C., to obtain a dispersion (X7-3). The viscosity of the(X7-3) was 20 mPa·s. The (X7-3) was charged into a vessel equipped witha stirrer and a thermometer, and then removal of solvent was carried outfor 2 hours at 30° C. After completion of removal of solvent, maturingwas carried out for 4 hours at 40° C., to obtain a dispersion (X7-4).The volume median particle diameter and the number median particlediameter of the (X7-4) were 5.13 μm and 4.63 m, respectively, which weremeasured using a Multisizer III. 100 parts of the (X7-4) wascentrifuged. After addition of 50 parts of water, solid-liquidseparation was carried out, and this process was repeated twice. Afterdrying for 24 hours at 40° C., resin particles (Y-7) were obtained. Thephysical properties of the (Y-7) are shown in Table 2.

Comparative Example 1

In a beaker, 140 parts of the urethane prepolymer (1) and 5 parts of thecuring agent (1) were mixed, and then 465 parts of water and 3 parts ofdodecylnaphthalenesulfonic acid sodium salt were added thereto. Then,they were mixed with an Ultra-disperser (manufactured by YamatoScientific Co., Ltd.) at 9,000 rpm for 20 minutes at 25° C., to obtainan aqueous dispersion (HX1-1).

100 parts of the (HX1-1) was centrifuged. After addition of 40 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After, drying for 1 hour at 35° C.,resin particles (HY-1) were obtained. The physical properties of the(HY-1) are shown in Table 2.

Comparative Example 2

In a beaker, 150 parts of the urethane prepolymer (1), 6 parts of thecuring agent (1), and 40 parts of ethyl acetate were mixed, and then 457parts of the dispersion (1) was added. Then, they were stirred with a TKHomomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 12,000 rpmfor 1 minute at 25° C., to obtain an aqueous dispersion (HX2-1).

100 parts of the (HX2-1) was centrifuged. After addition of 40 parts ofwater, solid-liquid separation was carried out by centrifugation, andthis process was repeated twice. After drying for 1 hour at 35° C.,resin particles (HY-2) were obtained. The physical properties of the(HY-2) are shown in Table 2. TABLE 1 Examples 1 2 3 4 5 Resin particles(Y-1) (Y-2) (Y-3) (Y-4) (Y-5) Shape factor (SF-1) 168 170 171 185 189Volume average particle 5.9 6.0 89 7.3 6.4 diameter of resin particles(μm) Average of surface 0.20 0.17 0.55 0.19 0.22 roughness (Ra) (μm) BETspecific surface area 3.2 3.0 2.3 3.5 3.9 (m²/g)

TABLE 2 Example Comparative Example 6 7 1 2 Resin particles (Y-6) (Y-7)(HY-1) (HY-2) Shape factor (SF-1) 190 180 102 103 Volume averageparticle 5.8 5.1 7.4 7.1 diameter of resin particles (μm) Average ofsurface 0.16 0.12 0.63 0.21 roughness (Ra) (μm) BET specific surfacearea 2.4 1.1 2.4 4.1 (m²/g)

INDUSTRIAL APPLICABILITY

1. According to the preparing method of resin particles of the presentinvention, it is possible to reduce the time for deforming resinparticles. Further, the deformed resin particles have excellent shapestability. Furthermore, since the preparing method of the presentinvention is carried out in an aqueous medium, it is very safe ascompared with conventional methods.

2. The resin particles obtained by the preparing method of the presentinvention are not spherical particles (but are spindle or rod-shapedparticles) so that they can have a very large surface area. Further, theresin particles of the present invention have a uniform particlediameter and excellent powder fluidity and storage stability.

Therefore, the resin particles of the present invention provide thefollowing effects.

Since the resin particles of the present invention are spindle orrod-shaped particles (that is, the SF-1 thereof ranges from 110 to 800),they show significant thixotropy when dispersed in a solvent or anaqueous medium. For this reason, the resin particles of the presentinvention can be suitably used as a fluidity improver for paint orcoating materials.

Further, the alignment of the resin particles in the formation of acoating layer is uniform in the direction of longer diameter of theresin particles. Therefore, the resin particles of the present inventionprovide the effect of preventing blister from occurring in forming acoating layer and the effect of improving luster or a gloss of acoating.

Furthermore, in a case where the resin particles of the presentinvention are blended in cosmetics such as lipstick and foundation, theyprovide smooth feeling when such cosmetics are applied to the skin.

Moreover, in a case where the resin particles of the present inventionare used as a toner, cleaning of the toner with a cleaning blade isfacilitated.

1. A method for preparing resin particles, comprising the steps of:applying a shear force to an aqueous dispersion (II) with increasedviscosity formed by adding a thickener (V) to an aqueous dispersion (I)containing resin particles (A); and decreasing the viscosity of theaqueous dispersion obtained by the step described above.
 2. The methodaccording to claim 1, wherein the viscosity of the aqueous dispersion isdecreased by adding a viscosity decreasing agent (E) in the viscositydecreasing step.
 3. The method according to claim 2, wherein theviscosity decreasing agent (E) is α-glycanase and/or β-glycanase.
 4. Themethod according to claim 1, wherein the viscosity of the aqueousdispersion (II) is in the range of 300 to 100,000 mPa·s (at 25° C.). 5.The method according to claim 1, wherein the viscosity of the aqueousdispersion after subjecting the viscosity decreasing step is 200 mPa·sor less (at 25° C.).
 6. The method according to claim 1, wherein thethickener (V) is at least one of naturally-occurring, semisynthetic, andsynthetic water-soluble polymers.
 7. The method according to claim 6,wherein the thickener (V) is at least one selected from the groupconsisting of acrylic acid-based (co)polymer salts, vinyl ether-based(co)polymers, and cellulose-based semisynthetic polymers.
 8. The methodaccording to claim 1, wherein the resin particles (A) comprises at leastone resin selected from the group consisting of vinyl resins,polyurethanes, epoxy resins, and polyesters.
 9. The method according toclaim 1, wherein the aqueous dispersion (I) is a product obtained byreacting an active group-containing prepolymer (α) with a curing agent(β) in an aqueous medium.
 10. The method according to claim 9, whereinthe reactive group-containing prepolymer (α) has at least one reactivegroup selected from the group consisting of an isocyanate group, ablocked isocyanate group and an epoxy group, and the curing agent (β) isan active hydrogen-containing compound (β1) that may be blocked with aremovable compound.
 11. The method according to claim 10, wherein theactive hydrogen-containing compound (β1) that may be blocked with aremovable compound is a ketimine compound and/or water.
 12. A reinparticle (B) obtained in accordance with the method of claim
 1. 13. Theresin particle (B) according to claim 12, which has a shape factor(SF-1) of 110 to
 800. 14. The resin particle (B) according to claim 13,which can be used as additives for paints, additives for coatingmaterials, powder coatings, additives for cosmetics, resins for slushmolding, spacers for use in manufacturing electronic components ordevices, standard particles for electronic measuring instruments, tonersfor electrophotography, toners for electrostatic recording, toners forelectrostatic printing, and hot-melt adhesives.